Andrea Ceglie

Particle size, charge and colloidal stability of humic acids coprecipitated with Ferrihydrite

Humic acids (HA) have a colloidal character whose size and negative charge are strictly dependent on surface functional groups. They are able to complex large amount of poorly ordered iron (hydr)oxides in soil as a function of pH and other environmental conditions. Accordingly, with the present study we intend to assess the colloidal properties of Fe(II) coprecipitated with humic acids (HA) and their effect on Fe hydroxide crystallinity under abiotic oxidation and order of addition of both Fe(II) and HA. TEM, XRD and DRS experiments showed that Fe-HA consisted of Ferrihydrite with important structural variations. DLS data of Fe-HA at acidic pH showed a bimodal size distribution, while at very low pH a slow aggregation process was observed. Electrophoretic zeta-potential measurements revealed a negative surface charge for Fe-HA macromolecules, providing a strong electrostatic barrier against aggregation. Under alkaline conditions HA chains swelled, which resulted in an enhanced stabilization of the colloid particles. The increasing of zeta potential and size of the Fe-HA macromolecules, reflects a linear dependence of both with pH. The increase in the size and negative charge of the Fe-HA precipitate seems to be more affected by the ionization of the phenolic acid groups, than by the carboxylic acid groups. The main cause of negative charge generation of Fe/HA is due to increased dissociation of phenolic groups in more expanded structure. The increased net negative surface potential induced by coprecipitation with Ferrihydrite and the correspondent changes in configuration of the HA could trigger the inter-particle aggregation with the formation of new negative surface. The Fe-HA coprecipitation can reduce electrosteric repulsive forces, which in turn may inhibit the aggregation process at different pH. Therefore, coprecipitation of Ferrihydrite would be expected to play an important role in the carbon stabilization and persistence not only in organic soils, but also in waters containing dissolved organic matter.

Effect of membrane composition on lipid oxidation in liposomes.

To study the effect of membrane composition on the oxidation of liposomes, different systems were prepared by adding one component at time to phosphatidylcholine (Epikuron 200). In particular, the effect of cholesterol and its ester, cholesterol stearate, on membrane structure and oxidation was studied. A first screening of the structure and net charge of the different preparation was made by means of z-potential and size measurements. Then the liposomes were oxidized by using a hydrophilic radical initiator, the (2,2-azobis(2-amidinopropane) hydrochloride, AAPH, which thermally decomposes to give a constant radical flux in water. The oxidation of liposomes, monitored by following the absorbance of the primary products of oxidation at 234 nm, was shown to be dependent on the composition of the liposomal bilayer and so on its biophysical properties. In addition, size and z-potential measurements gathered in the time course of the peroxidation reaction, revealed that the oxidation induced a modification of the superficial characteristics of the membrane bilayer so as to change its charge at the shear plane (z-potential). This behaviour was shared by all liposomal preparations independent of the composition. The change in sizes of the different liposomal preparation, instead, followed different trends, being more stable both in control samples and in oxidized ones when cholesterol was present. From the analysis of the results, it can be concluded that cholesterol affects the oxidation induced by hydrophilic radical initiator of model membranes by changing the biophysical properties of the phospholipid bilayer. The rigidity induced by cholesterol at temperatures above the T(m) makes the membrane more resistant to radical attack from an external aqueous phase and this in turn delays the start of the reaction. The decrease of z-potential of the liposomal particles induced by the oxidation process can be an important clue to understand the mechanisms involved in the etiology of important diseases.

Effects of sulfate ions and slightly acidic pH conditions on Cr(VI) adsorption onto silica gelatin composite

The feasibility of utilizing CTAB-silica gelatin composite (C-SGC) to remove hexavalent chromium from aqueous solutions under different conditions was investigated. Removal of chromate was assessed through evaluation of the adsorption kinetics of chromate ions on the composite under equilibrium conditions in the presence of sulfate ions and at a slightly acidic pH condition (pH 5.8). Adsorption competition tests in the presence of sulfate ions showed that Cr(VI) was still effectively adsorbed from aqueous solution regardless of the presence of the competing anions. In fact, the adsorption kinetics performed at different initial chromate concentrations were unaffected by the presence of 100 mg L(-1) sulfate ions (pH 7.5). The equilibrium adsorption data were fitted by Freundlich adsorption isotherms which confirmed that the adsorption efficiency of chromium on the CTAB-silica gelatin composite was unchanged in the presence of sulfate ions. Further, the adsorption process was shown to be pH dependent and more efficient at slightly acidic pH (5.8). These findings demonstrated a high specificity of the CTAB-silica gelatin composite for chromium, and highlight the possibility of using this matrix for efficient removal of chromium from industrial wastewater without the need to eliminate contaminant sulfate ions.

Nucleotides and nucleolipids derivatives interaction effects during multi-lamellar vesicles formation.

In this paper a micellar interface, constituted by the cationic surfactant CTAB, in presence of 1,2-epoxydodecane and nucleotides was used for catanionic multi-lamellar vesicles (MLVs) formation. The micellar solution of CTAB is able to disperse the 1,2 epoxydodecane in the micellar core promoting the reaction of this reagent with the nucleotide attracted by the positive surface charge of the micellar aggregates. The alkylation of AMP and UMP nucleotides leads to the synthesis of nucleolipids. The behaviour of the supramolecular structures formed depends on the starting reagents (AMP, UMP and AMP+UMP) and on the assembly capabilities of the products. In particular nucleotides and nucleotides derivatives interaction effects are evaluated during the multi-lamellar vesicles formation. NMR spectroscopy and UV-vis measurements performed on MLVs showed strong aryl interactions. Interestingly, NMR spectra revealed prevailing stacking interactions between complementary nucleolipids. The assembly of complementary nucleotides affects the course of the reaction during the MLVs formation. Moreover the MLVs supramolecular stability has been tested by means of turbidity and UV-vis measurements. In particular, an enhanced stability has been found in systems prepared with complementary nucleotides confirming that in these systems the self-assembly process is influenced by nucleolipids interactions. Furthermore by following the hypocromic effect during the micellar catalysis, we showed that even in the earlier stages of the reaction significant differences are detectable.

The role of the cosurfactant in the CTAB/water/n-pentanol/n-hexane system: Pentanol effect on the phase equilibria and mesophase structure

We report on the effect of 1-pentanol loading on the phase behaviour of mixtures of CTAB/water/n-hexane at fixed mole ratios 1∶80∶47. The cosurfactant induces changes in the interfacial film curvature. By increasing the pentanol/CTAB mole ratio, the system evolves from oil-in-water to water-in-oil structures. For very large 1-pentanol loading some water is expelled from the reverse micelles resulting in a L2plus water equilibrium (emulsification failure). In the range of compositions investigated most of the phase equilibria reveals the coexistence of liquid crystals and hexane/pentanol solutions. In these cases, we estimate the interface composition by assuming a constant 1-pentanol concentration in all the oil domains, and by tacking into account the alcohol solubility in water. In the case of single-phase sample the interfacial composition was determined by means of turbidimetric titration. The adsorption of cosurfactant at the interface of direct micelles, planar lamellae, bicontinuous microemulsions, and spherical reverse micelles follows the same adsorption isotherm (independently from the curvature of the interface). Moreover, the results obtained unambiguously show that the interface composition dictates the spontaneous curvature of interfacial film. Actually positive, null, and negative curvatures correspond to different compositions of the interfacial film. Once the influence of cosurfactant on the spontaneous curvature of the interface is understood, the appearance of the emulsification failure upon pentanol loading can be rationalised within the framework of the flexible surface model.

Phyto-liposomes as nanoshuttles for water-insoluble silybin-phospholipid complex.

Among various phospholipid-mediated drug delivery systems (DDS) suitable for topic and oral administration, phytosome technology represents an advanced innovation, widely used to incorporate standardized bioactive polyphenolic phytoconstituents into phospholipid molecular complexes. In order to extend their potential therapeutic efficiency also to other routes of administration, we proposed a novel phytosome carrier-mediated vesicular system (phyto-liposome) as DDS for the flavonolignan silybin (SIL), a natural compound with multiple biological activities related to its hepatoprotective, anticancer and antioxidant (radical scavenging) effects. We screened the optimum fraction of its phytosome, available in the market as Siliphos™, into liposomes prepared by extrusion, such that vesicle sizes and charges, monitored through dynamic light scattering and laser doppler velocimetry, satisfied several quality requirements. Special emphasis was placed on the study of host-guest interaction by performing UV-vis absorption, spectrofluorimetry and NMR experiments both in aqueous and non-polar solvents to probe the effect of the presence of phospholipids on the electronic properties of SIL and its propensity to engage H bonding with the lipid headpolar groups. Finally, fluorescence microscopy observations confirmed the ability of phyto-liposomes to be internalized in human hepatoma cells, which was promising for their potential application in the treatment of acute or chronic liver diseases.

Specific interactions between nucleolipid doped liposomes and DNA allow a more efficient polynucleotide condensation.

The interactions between cationic liposomes doped with the anionic nucleolipid 1,2-dipalmitoyl-sn-glycero-3-cytidine diphosphate (DP-Cyt) and deoxyribonucleic acid (DNA) were investigated. Toward this goal, new liposomal and lipoplex formulations characterized by the presence of the anionic amphiphile DP-Cyt were proposed. The effects of incorporation of the cytosine functionalized lipid DP-Cyt into the cationic bilayers were analyzed by means of electrophoretic mobility, dynamic light scattering (DLS) and fluorescence spectroscopy techniques. These approaches allowed us to follow the DNA condensation process and to identify specific electrokinetic characteristics of liposome and DNA-liposome complexes formation. Specifically, DP-Cyt liposomes and DNA were shown to form electrically stable or unstable complexes depending on the charge ratio between the phosphate group of DNA and the cationic lipid. Remarkably, a prominent role for DP-Cyt in enhancing the DNA binding capacity on liposomes was demonstrated. Zeta potential experiments performed on systems with different liposomes/DNA ratio showed that the value of the charge neutralization point is a function of the content of the incorporated DP-Cyt. As a whole, our data demonstrate that the association of cationic DP-Cyt doped liposomes with DNA is driven by both electrostatic interaction and additional specific interactions at the polar head level based on the cytidine nucleobase.

Release of small hydrophilic molecules from polyelectrolyte capsules: Effect of the wall thickness.

Polymer nanocapsules assembled on cationic liposomes have been built through the layer-by-layer (LbL) technique. Chitosan and alginate, two biocompatible polyelectrolytes, were used to cover the template, where the Rhodamine B was previously loaded. The multishell formed with the alternate deposition of the polyelectrolytes, according to the principles of the LbL assembly, was supposed to change the permeability of the capsule wall. The thickness of the multishell was seen increasing with the number of layers deposited through the observations with the Transmission Electron Microscope. The permeability of the capsules was studied through Rhodamine B release assays. Nanocapsules with seven layers of polyelectrolytes released the dye slowly compared to the capsules with three or five layers. The Ritger-Peppas model was applied to investigate the release mechanisms and a non-Fickian transport behavior was detected regardless of the number of layers. Values of diffusion coefficients of Rhodamine B through the capsule wall were also calculated.

Impact of antioxidants dispersions on the stability and oxidation of water-in-olive-oil emulsions

Water-in-olive-oil emulsion stability was studied as a function of the composition of the water dispersed phase. In particular, different polyphenolic extracts from natural sources were dispersed in the olive oil and their impact on emulsion kinetic stability and susceptibility to oxidation was evaluated. As natural sources, extra virgin olive oil, olive mill waste and green tea leaves were chosen. To test their impact on emulsion properties, the emulsions were prepared with fixed aqueous phase content. As emulsifiers, a fixed percentage of a mixture Span 80 (sorbitan monoleate)/Tween 80 (polysorbate 80) was used. The effect of the antioxidant dispersion on emulsion oxidation was studied by triggering the oxidation reaction in the oil phase with the lipophilic radical initiator AMVN (2,2-azobis(2,4-dimethylvaleronitrile). Then, the oxidation reaction was followed by using diphenyl-1-pyrenylphosphine, which becomes fluorescent when it is oxidized by hydroperoxides. The impact of antioxidant dispersions on emulsion kinetic stability was studied by UV–Vis turbidity measurements. The oxidation results were correlated to antioxidant extracts oxygen radical adsorption capacity (ORAC) and to emulsion kinetic stability. On the whole, antioxidants dispersions delayed the oxidation reaction to different extents in dependence on their ORAC values and their components amphiphilicity. Remarkably, among the antioxidants tested, the aqueous polyphenol extract from virgin olive oil was the most effective because it protected emulsions both from oxidation and from phase separation. Additionally, from this set of experiments, the primary role of the interfacial properties of olive oil polyphenols was highlighted.

Visible light caffeic acid degradation by carbon-doped titanium dioxide

The removal of the phenolic compound, caffeic acid, by photodegradation has been investigated using carbon-doped titanium dioxide particles as a photocatalyst under visible light. UV-vis absorption spectroscopy and gas chromatography-ion trap mass spectrometry analyses revealed a substrate concentration dependence of the removal of caffeic acid from a water solution. The k2 and t(0.5) parameters of each reaction were calculated by fitting kinetics data to a second-order kinetic adsorption model. To evaluate the photodegradation event, the effect of the adsorption process on the whole degradation was also monitored in the absence of light. Adsorption isotherm studies supported by ζ potential and scanning electron microscopy data demonstrated the pivotal role of the absorption mechanism. It was found that the whole photodegradation process is governed by a synergic mechanism in which adsorption and photodegradation are involved. This study, centered on the removal of caffeic acid from aqueous solutions, highlights the potential application of this technology for the elimination of phenolic compounds from olive mill wastewater, a fundamental goal in both the agronomical and environmental fields.