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Study of micro and nano surface structures from UV irradiated urethane/urea elastomers.

In this work we address new results obtained with a thin free standing flexible film (approximately 120 microm) of a urethane/urea copolymer related to the formation of micro and nano size structures [M.H. Godinho, A.C. Trindade, J.L. Figueirinhas, L.V. Melo, P. Brogueira, Synthetic Metals, 147(1-3), 209 (2004); M.H. Godinho, A.C. Trindade, J.L. Figueirinhas, L.V. Melo, P. Brogueira, Molecular Crystals and Liquid Crystals (2005)]. The copolymer was synthesized from a polypropylene oxide-based prepolymer with three isocyanate terminal groups (PU) and polybutadienediol (PBDO) with PBDO content of 40% wt. After casting and curing the film was cut into different samples and each exposed to UV radiation for different periods of time; 23, 25, 26, 31 and 49 h (lambda=254 nm) and later extracted with toluene and dried. The dried films were then studied by polarising optical microscopy (POM), small angle light scattering (SALS) and the surfaces exposed to UV radiation analyzed by means of atomic force microscopy (AFM). Before extraction with toluene a nanometer-flat surface, characterized by a mean roughness value Ra=0.59 nm, was obtained. Depending on exposure time to UV radiation and after extraction with toluene a corrugated surface, with features mum-sized in all axes, resulting in an increase of the overall mean roughness value to Ra=50.7 nm, starts to develop after 25 h of exposure time. This work gives evidence of the non-monotonous time behavior of the wrinkled surface growth that develops under the action of ultraviolet radiation. As the exposure time increases the free-standing films directly exposed surfaces show a decreasing density of the structures observed and an increasing characteristic peak-to-valley height. The peak-to-valley height measured for samples exposed for 23, 25, 26, 31 and 49 h, respectively 193, 383, 381, 1550 and 2039 nm and the corresponding mean roughness values are Ra=50.7 nm, 105.4, 116.8, 438.3 and 515.4 nm, respectively. Between 26 and 31 h exposure time a leap in both values, peak-to-valley and Ra, was observed. The sudden increase in these values is correlated to fabrication of wrinkles by uniaxially stretching PU/PBDO elastomer films.

Biocompatible Materials↗

Cyclic loading response of bioprosthetic heart valves: effects of fixation stress state on the collagen fiber architecture.

Biologically derived, chemically modified collagenous tissues are being increasingly used to fabricate cardiac valve prostheses and as biomaterials in cardiovascular repair. A stress-free state during chemical modification has been shown to preserve the collagen fiber architecture of the native tissue, potentially preserving native mechanical properties and improving prostheses durability. However, it is not known if the native collagen fiber architecture is stable during long-term in vivo operation. To address this question, we obtained porcine aortic valves chemically treated at (i) 0 mmHg transvalvular pressure (with 40 mmHg aortic pressure) and (ii) 4 mmHg transvalvular pressure, then subjected the valves to 0, 1 x 10(6), 50 x 10(6), and 200 x 10(6) in vitro accelerated wear testing (AWT) cycles. The resulting changes in collagen fiber architecture were quantified using small angle light scattering analysis (SALS). SALS measurements indicated that collagen fibers in the 0 mmHg pressure-fixed leaflets became more aligned between 1 x 10(6) and 50 x 10(6) AWT cycles. In contrast, only minor changes (not statistically significant) in collagen fiber orientation occurred in the 4 mmHg pressure-fixed valvular tissue with cycling. It was also noted that although the 0 mmHg group was fixed without transvalvular pressure, distention of the root induced significant changes in collagen structure of the leaflets. Overall, our observations suggest that the native collagen fiber crimp of the 0 mmHg pressure-fixed leaflets were rapidly lost after only 50 x 10(6) AWT cycles (equivalent to approximately 1.6 patient years) and thus may not be maintained over a sufficient period of time to be clinically beneficial. Further, the collagen structure of the native aortic valve is exquisitely sensitive to dimensional change in the aortic root-independent of the presence of transvalvular pressure. Our findings also suggest that without in vivo remodeling, any collagenous tissue used to fabricate BHV may undergo similar degenerative, irreversible changes in vivo.

Aortic Valve↗

Influence of N-dodecyl-N,N-dimethylamine N-oxide on the activity of sarcoplasmic reticulum Ca(2+)-transporting ATPase reconstituted into diacylphosphatidylcholine vesicles: efects of bilayer physical parameters.

Sarcoplasmic reticulum Ca-transporting ATPase (EC 3.6.1.38) was isolated from rabbit white muscle, purified and reconstituted into vesicles of synthetic diacylphosphatidylcholines with monounsaturated acyl chains using the cholate dilution method. In fluid bilayers at 37 degrees C, the specific activity of ATPase displays a maximum (31.5+/-0.8 IU/mg) for dioleoylphosphatidylcholine (diC18:1PC) and decreases progressively for both shorter and longer acyl chain lengths. Besides the hydrophobic mismatch between protein and lipid bilayer, changes in the bilayer hydration and lateral interactions detected by small angle neutron scattering (SANS) can contribute to this acyl chain length dependence. When reconstituted into dierucoylphosphatidylcholine (diC22:1PC), the zwitterionic surfactant N-dodecyl-N,N-dimethylamine N-oxide (C12NO) stimulates the ATPase activity from 14.2+/-0.6 to 32.5+/-0.8 IU/mg in the range of molar ratios C12NO:diC22:1PC=0/1.2. In dilauroylphosphatidylcholines (diC12:0PC) and diC18:1PC, the effect of C12NO is twofold-the ATPase activity is stimulated at low and inhibited at high C12NO concentrations. In diC18:1PC, it is observed an increase of activity induced by C12NO in the range of molar ratios C12NO:diC18:1PC< or =1.3 in bilayers, where the bilayer thickness estimated by SANS decreases by 0.4+/-0.1 nm. In this range, the 31P-NMR chemical shift anisotropy increases indicating an effect of C12NO on the orientation of the phosphatidylcholine dipole N(+)-P- accompanied by a variation of the local membrane dipole potential. A decrease of the ATPase activity is observed in the range of molar ratios C12NO:diC18:1PC=1.3/2.5, where mixed tubular micelles are detected by SANS in C12NO+diC18:1PC mixtures. It is concluded that besides hydrophobic thickness changes, the changes in dipole potential and curvature frustration of the bilayer could contribute as well to C12NO effects on Ca(2+)-ATPase activity.

Animals↗

Production of soybean phosphatidylcholine-chitosan nanovesicles by reverse phase evaporation: a step by step study.

In the present work, we describe the preparation of composite nanovesicles containing soybean phosphatidylcholine and polysaccharide chitosan by the reverse phase evaporation method. Nanovesicles free from chitosan prepared in the same way were studied as reference. The production method involves the preparation of reverse micelles followed by the formation of an organogel, which is dispersed in water to yield the final liposomal structures. Structural changes in each step of the nanovesicles preparation were studied by means of static and dynamic light scattering as well as small angle X-ray scattering. Chitosan was also fully characterized in solution. The hydrodynamic radius of the composite nanovesicles is in the range of 174-286 nm, depending on the chitosan contents. A comparison with nanovesicles free from chitosan indicates the existence of higher contents of multilamellae structures in the composites, as well as improved stability in water.

Acetates↗

Influence of phytosphingosine-type ceramides on the structure of DMPC membrane.

The present paper describes the influence of the ceramides with phytosphingosine base, N-stearoylphytosphingosine (Cer[NP]) and alpha-hydroxy-N-stearoylphytosphingosine (Cer[AP]), on the structure and properties of multilamellar (MLVs) and unilamellar vesicles (ULVs) of dimyristoylphosphatidylcholine (DMPC). The lamellar repeat distance, D, has been measured at various temperatures using small angle X-ray diffraction. The incorporation of ceramides into the DMPC membrane causes larger D compared to pure DMPC membrane. For both ceramide types, at 32 degrees C, there is a linear relationship between the D value and the ceramide concentration. However, there is no such dependence at 13 or 60 degrees C. Unlike Cer[AP], Cer[NP] induces a new phase with a repeat distance of 38.5A. The membrane thickness and the vesicle radius of ULVs in water and in sucrose solution were calculated from small angle neutron scattering curves. Phytosphingosine ceramides increase both the membrane thickness and the radius in comparison to pure DMPC ULVs. The stability of ULVs in time was studied by dynamic light scattering. Both ceramides induce an aggregation of the ULVs into micrometer sized non-multilamellar structures in pure water. Presence of sucrose in the environment averts the vesicle aggregation.

Ceramides↗

Nature and properties of ionomer assemblies. II.

The principle subject in the current paper is to summarize and characterize the ionomers based on polymers and copolymers such as polystyrene (PSt), polyisoprene (PIP), polybutadiene (PB), poly(styrene-b-isobutylene-b-styrene) (PSt-PIB-PSt), poly(butadiene-styrene) (PB-PSt), poly(ethylene terephthalate) (PET), poly(butylene adipate) (PBA), poly(butylene succinate) (PBSi), poly(dimethylcarbosiloxanes), polyurethane, etc. The self-assembly of ionomers, models concerning ionomer morphologies, physical and rheological properties of ionomer phase and percolation behavior of ionomers were discussed. The ionomer phase materials and dispersions have been characterized by differential scanning calorimetry (DSC), small-angle X-ray catering (SAXS), small-angle neutron scattering (SANS), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), etc. The wide range of compositions, molecular architectures, and morphologies present in ionomeric disperse systems are of great interest. The research is particularly devoted to the potential application of these materials and an understanding of the fundamental principles of the ionomers. They are extremely complex systems, sensitive to changes in structure and composition, and therefore not easily amenable to modeling and to the derivation of general patterns of behavior. The reviewed data indicate that a large number of parameters are important in influencing multiplet formation and clustering in random ionomers. Among these are the ion content, size of the polyion and counterion, dielectric constant of the host, T(g) of the polymer, rigidity or persistence length of the backbone, position of the ion pair relative to the backbone, steric constraints, amount and nature of added additive (plasticizer), thermal history, etc.

Polymers↗

Importance of head group polarity in controlling aggregation properties of cationic gemini surfactants.

Cationic gemini surfactants have been extensively studied in the recent past and the effect of chain length, spacer length and nature on aggregation behavior has been examined. But the effect of variation in head group polarity on micellization has not been examined. Hence, the effect of head group polarity of the butane-1,4-bis(dodecyldimethylammonium bromide) surfactants on aggregation properties is studied through conductance, surface tension, viscosity, and small-angle neutron scattering (SANS) measurements. The critical micellar concentration (cmc), average degree of micelle ionization (beta(ave)), minimum area per molecule of surfactant at air-water interface (A(min)), surface excess concentration (Gamma(max)) and Gibbs free energy change of micellization (DeltaG degrees (mic)) of the surfactants were determined from conductance and surface tension data. The aggregation numbers (N), dimension of micelle (b/a), effective fractional charge per monomer (alpha) were determined from SANS and hydration of micelle (h(m)) from viscosity data. The increasing head group polarity of gemini surfactant having spacer chain length of 4 methylene units promotes micellar growth, leading to decrease in cmc, beta(ave), DeltaG degrees (mic) and increase in N and b/a. This is well supported by the observed increase in hydration (h(m)) of micelle with increase in aggregation number (N) and dimension (b/a) of micelle. The Kraft temperature (k(T)), foamability and foam stability as a function of head group polarity of gemini surfactants were also examined.

Cations↗

Advances in adsorption of surfactants and their mixtures at solid/solution interfaces.

Surfactants and their mixtures can drastically change the interfacial properties and hence are used in many industrial processes such as dispersion/flocculation, flotation, emulsification, corrosion inhibition, cosmetics, drug delivery, chemical mechanical polishing, enhanced oil recovery, and nanolithography. A review of studies on adsorption of single surfactant as well as mixtures of various types (anionic-cationic, anionic-nonionic, cationic-nonionic, cationic-zwitterionic and nonionic-nonionic) is presented here along with mechanisms involved. Results obtained using techniques such as zeta potential, flotation, AFM, specular neutron reflectivity, small angle neutron scattering, fluorescence, ESR, Raman spectroscopy, ellipsometry, HPLC and ATR-IR are reviewed along with those from traditional techniques to elucidate the mechanisms of adsorption and particularly to understand synergistic/antagonistic interactions at solution/liquid interfaces and nanostructures of surface aggregates. In addition, adsorption of several mixed surfactant systems is considered due to their industrial relevance. Finally an attempt is made to derive structure-property relationships to provide a solid foundation for the design and use of surfactant formulations for industrial applications.

Journal Article↗

Viscoelastic and structural properties of pharmaceutical hydrogels containing monocaprin.

The purpose of this study was to characterize the rheological and structural properties of a pharmaceutical multicomponent hydrogel formulation. This formulation consists of a hydrogel-forming poly(acrylic acid) polymer (Carbopol 974P), microbicide (monocaprin), non-ionic surfactant (Tween 20 or Tween 40), and preservatives. The effects of surfactant addition, monocaprin concentration, and pH on the formulation are investigated with the aid of various rheological methods and small angle neutron scattering (SANS). A change of pH from 4 (reduced electrostatic interactions) to higher pH values (prominent electrostatic forces) resulted in a marked impact on both the structural and rheological characteristics, with higher values of the dynamic moduli. At pH 4, the rheological features were strongly influenced by the addition of surfactant and monocaprin concentration, whereas at higher values of pH the effect of additives was modest. The picture that emerges from SANS and rheology is that enhanced association structures evolve at pH 4, while at higher pH the tendency to form associations is inhibited. At all the conditions, the rheological results suggest a viscoelastic solid behavior, which is typical for many gels.

Elasticity↗

Fractal nature of chromatin organization in interphase chicken erythrocyte nuclei: DNA structure exhibits biphasic fractal properties.

Arrangement of chromatin in intact chicken erythrocyte nuclei was investigated by small angle neutron scattering. The scattering spectra have revealed that on the scales between 15 nm and 1.5 microm the interior of the nucleus exhibited properties of a mass fractal. The fractal dimension of the protein component of cell nucleus held constant at approximately 2.5, while the DNA organization was biphasic, with the fractal dimension slightly higher than 2 on the scales smaller than 300 nm and approaching 3 on the larger scales.

Animals↗

Interfacial tension of aqueous biopolymer mixtures close to the critical point.

Proteins and polysaccharides, being the main constructional materials in many biological structures, have a limited compatibility in aqueous media. At sufficiently high concentrations, they form water-in-water emulsions. Interfacial tension is an important parameter in such systems since it is a controlling factor in the morphology development during processing. In this work a rheo-optical methodology, based on the analysis of small angle light scattering (SALS) patterns during fibril break-up, is used to study the interfacial tension of water-sodium caseinate-sodium alginate systems located close to and relatively far from the binodal. The interfacial tension close to the critical point was approximately 10(-8) N/m, and it increased considerably, to a value of up to 5.2 x 10(-6) N/m farther from the critical point. For the scaling of the interfacial tension with the density difference between the phases, a scaling exponent of 3.1 +/- 0.3 was found, in agreement with the critical mean-field scaling exponent of 3.

Alginates↗

Microscopic structure of gelatin coacervates.

Microscopic structure of simple coacervates of gelatin having concentration approximately 130 g/l were studied at 25 degrees C by atomic force microscopy (AFM), rheology, small angle neutron scattering (SANS), UV absorption and circular dichroism (CD) techniques. The behavior of viscoelastic exponents Delta' and Delta'' of storage and loss modulii (G'(omega) approximately omega Delta', G''(omega) approximately omega Delta") revealed that, Delta' = 0.25+/-0.01 and Delta'' = 0.78+/-0.1 for coacervates. The mass fractal dimension 'd(f)' for coacervate was found to be 2.27, which attributed a compact heterogeneous network structure to the coacervates. This is supported by AFM pictures. The CD and UV absorption data indicated presence of helical structures inside the coacervates phase. SANS results showed the existence of a single length scale associated with this system identified as gelatin persistence length, zeta = 27+/-2 A. These studies indicate that the coacervate phase is a low dimensional dense heterogeneous material comprised of strongly interconnected triple helices which imparts a large storage modulus to this material.

Circular Dichroism↗

Structural and thermodynamic properties of starches extracted from GBSS and GWD suppressed potato lines.

A combined DSC-SAXS approach was employed to study the effects of amylose and phosphate esters on the assembly structures of amylopectin in B-type polymorphic potato tuber starches. Amylose and phosphate levels in the starches were specifically engineered by antisense suppression of the granule bound starch synthase (GBSS) and the glucan water dikinase (GWD), respectively. Joint analysis of the SAXS and DSC data for the engineered starches revealed that the sizes of amylopectin clusters, thickness of crystalline lamellae and the polymorphous structure type remained unchanged. However, differences were found in the structural organization of amylopectin clusters reflected in localization of amylose within these supramolecular structures. Additionally, data for annealed starches shows that investigated potato starches possess different types of amylopectin defects. The relationship between structure of investigated potato starches and their thermodynamic properties was recognized.

Amylopectin↗

Effect of anti-inflammatories on Pluronic F127: micellar assembly, gelation and partitioning.

We present results on the effect of two anti-inflammatory agents, naproxen and indomethacin, on the structure, assembly and gelation transitions of Pluronic F127 micelles. Small-angle neutron scattering experiments on micellar solutions indicate that the micelle aggregation number decreases significantly in the presence of drug solutes, causing the number density of micelles to increase. However, only slight changes were observed in the critical micelle concentration of F127 in the presence of these drugs. Both anti-inflammatory agents were found to shift the liquid-to-gel and gel-to-liquid transitions of the copolymer to lower temperatures. This may be the result of an increase in the micellar volume fraction, caused by the presence of the hydrophobic drugs. Using an ultraviolet spectroscopy technique, we have also measured the solubilities and micelle-water partition coefficients (Kmw) of naproxen and indomethacin in water and F127 solutions. The values of Kmw for naproxen and indomethacin are 355 +/- 64 and 474 +/- 33, respectively. They are larger than previously reported lipid-water partition coefficients, indicating that F127 micelles may be a better choice for drug loading than lipid vesicles. The slightly greater effects of indomethacin on the gelation boundary as compared with naproxen may be attributable to a higher value of Kmw.

Anti-Inflammatory Agents↗

Guidance of engineered tissue collagen orientation by large-scale scaffold microstructures.

The tensile strength and stiffness of load-bearing soft tissues are dominated by their collagen fiber orientation. While microgrooved substrates have demonstrated a capacity to orient cells and collagen in monolayer tissue culture, tissue engineering (TE) scaffolds are structurally distinct in that they consist of a three-dimensional (3-D) open pore network. It is thus unclear how the geometry of these open pores might influence cell and collagen orientation. In the current study we developed an in vitro model system for quantifying the capacity of large scale ( approximately 200 microm), geometrically well-defined open pores to guide cell and collagen orientation in engineered tissues. Non-degradable scaffolds exhibiting a grid of 200 microm wide rectangular pores (1:1, 2:1, 5:1, and 10:1 aspect ratios) were fabricated from a transparent epoxy resin via high-resolution stereolithography. The scaffolds (n=6 per aspect ratio) were surface modified to support cell adhesion by covalently grafting GRGDS peptides, sterilized, and seeded with neonatal rat skin fibroblasts. Following 4 weeks of static incubation, the resultant collagen orientation was assessed quantitatively by small angle light scattering (SALS), and cell orientation was evaluated by laser confocal and scanning electron microscopy. Cells adhered to the struts of the pores and proceeded to span the pores in a generally circumferential pattern. While the cell and collagen orientations within 1:1 aspect ratio pores were effectively random, higher aspect ratio rectangular pores exhibited a significant capacity to guide global cell and collagen orientation. Preferential alignment parallel to the long strut axis and decreased spatial variability were observed to occur with increasing pore aspect ratio. Intra-pore variability depended in part on the spatial uniformity of cell attachment around the perimeter of each pore achieved during seeding. Evaluation of diamond-shaped pores [Sacks, M.S. et al., 1997. J. Biomech. Eng. 119(1), 124-127] suggests that they are less sensitive to initial conditions of cell attachment than rectangular pores, and thus more effective in guiding engineered tissue cell and collagen orientation.

Animals↗

Characterization of the pores in hydrous ferric oxide aggregates formed by freezing and thawing.

Hydrous ferric oxides (HFO) are efficient sorbents for inorganic and organic pollutants and therefore have great potentials in environmental science and engineering applications. Freezing and thawing of HFO suspensions leads to the formation of dense HFO aggregates. It facilitates the handling and increases the drying rate of HFO. In this study, we used a combination of pycnometry, gas adsorption (N(2) gas, water vapor), and small-angle neutron scattering (SANS) to characterize the porosity and pore size distribution of dense HFO aggregates formed by freezing dialyzed HFO suspensions at -25 degrees C and thawing them at room temperature. The crystallinity of the HFO, which was a 2-line ferrihydrite, was not affected by this treatment. Wet sieving and laser diffraction analysis showed that the dense HFO aggregates had a unimodal size distribution with an average diameter of 235+/-35 microm. Increasing the freezing rate by cooling with liquid N(2) (-196 degrees C) resulted in much smaller aggregates with an average diameter of 20 microm. Adding NaNO(3) electrolyte to the HFO suspensions prior to freezing also resulted in the formation of smaller aggregates. The dense HFO aggregates formed at -25 degrees C had a porosity of 0.73+/-0.02 ll(-1). SANS revealed a unimodal size distribution of pores, with an average pore diameter of 2.0 nm. The diameter of the HFO crystallites was estimated by transmission electron microscopy to be 1.9+/-0.5 nm. Geometrical considerations taking into account the unit particle and average pore size suggest that the crystallites retain 1-2 layers of hydration water during the coagulation induced by freezing. Analysis by N(2) gas adsorption showed that drying the dense HFO aggregates induced a reduction in porosity by about 25% and shifted the pore size distribution to smaller diameters. Rewetting during water vapor adsorption did not induce significant changes of the aggregate structure. The specific surface area of the dry HFO aggregates was between 320 and 380 m(2)g(-1).

Journal Article↗

Rheology of aqueous carbon black dispersions.

The interaction of carbon black with an acrylic resin has been investigated by rheology. Two carbon blacks, with similar particle size and surface characteristics but quite different particle morphologies, have been examined. These are somewhat arbitrarily denoted as "spherical" and "fractal" as shown by small-angle neutron scattering (SANS) and ultrasonic spectroscopy studies. In the absence of polymer, stable aqueous dispersions could not be obtained. Stable dispersions could be obtained, however, upon addition of polymer to a level corresponding to a ratio of 50 mg of polymer per 13 m2 (+/- m2) of surface area (i.e., 15 wt% particles). These stable dispersions exhibit flow typical of concentrated dispersions-Newtonian behavior up to some apparent "yield" or critical value, above which pronounced shear thinning is observed. The critical stress increases with increasing polymer concentration. When a significant amount of nonadsorbed polymer is also present, a second Newtonian plateau is superimposed on the shear-thinning behavior. This feature is observed for both particle types but is more pronounced for the fractal particle. When there is little or no nonadsorbed polymer, the viscosity of the fractal particle dispersions is greater than the viscosity of the spherical particle dispersions. At low polymer concentrations, the dispersions are predominantly viscous at low shear stresses. The phase angle decreases significantly over a narrow shear stress range and the rheology tends to more elastic behavior. At higher shear stresses, the dependence on particle morphology is weak.

Journal Article↗

Electrorheological properties and microstructure of silica suspensions.

We present experimental and theoretical results on the electrorheological response and microstructure of colloidal suspensions composed of silica nanoparticles dispersed in a silicon oil, as a function of electric field strength and silica water content. Using small-angle neutrons scattering experiments, we determined the evolution of the static structure factor of the suspensions when an electric field is applied. Experimental data were fitted with model calculations using the Percus-Yevick solution for Baxter's hard-sphere adhesive potential. The obtained stickiness parameter is directly related to the polarization interactions that depend on the water content of silica particles. The influence of the polarization interparticle potential on the rheology of the silica dispersions was investigated in a second time. A microscopic theory for the shear viscosity of adhesive hard-sphere suspensions was successfully used which describes the steady shear viscosity of suspension in terms of the fractal concept.

Journal Article↗