Paula V. Messina

Interactions between DMPC liposomes and the serum blood proteins HSA and IgG.

The interaction between two serum blood proteins, namely human serum albumin (HSA) and human immunoglobulin G (IgG), with 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) liposomes has been studied in detail using dynamic light scattering, flow cytometry, enzyme-linked immunosorbent assay (ELISA), electrophoretic mobility, differential scanning calorimetry (DSC), and surface tension measurements. HSA and IgG interact with liposomes forming molecular aggregates that remain stable at protein concentrations beyond those of total liposome coverage. Both HSA and IgG penetrate into the liposome bilayer. An ELISA assay indicates that the Fc region of IgG is the one that is immersed in the DMPC membrane. The liposome-protein interaction is mainly of electrostatic nature, but an important hydrophobic contribution is also present.

Manipulating the bioactivity of hydroxyapatite nano-rods structured networks: Effects on mineral coating morphology and growth kinetic

BACKGROUND Nano-hydroxyapatite particles have better bioactivity than the coarse crystals. So, they can be utilized for engineered tissue implants with improved efficiency over other materials. The development of materials with specific bioactive characteristics is still under investigation. METHODS The surface properties of four hydroxyapatite materials templated by different micelle-polymer structured network are studied. The synergistic interaction of each block copolymer in contact with CTAB rod-like micelles results in crystalline HAp nano-rods of 25-50nm length organized in hierarchical structures with different micro-rough characteristics. RESULTS It was observed that the material in vitro bioactivity strongly depends on the surface structure while in a minor extent on their Ca/P ratio. So, MIII and MIV materials with Skewness parameter Rsk>2.62 favored the formation on their surfaces of net-like phase with a high growth kinetic constant; while MI and MII (Rsk≤2.62) induced the appearance of spherulitic-like structures and a growth rate 1.75 times inferior. Material biocompatibility was confirmed by interaction with rat calvarial osteoblasts. CONCLUSIONS The different structures growth is attributed to a dissimilar matching of crystal planes in the material and the apatite layer formed. In specific synthesis conditions, a biocompatible material with a Ca/P ratio close to that for the trabecular bone and a morphology that are considered essential for bone-bonding was obtained. GENERAL SIGNIFICANCE The creation of implantable devices with a specific bioactive characteristic may be useful to manipulate the attachment of cells on mineral coating directly affecting the stability and life of the implant.

Photocatalytic degradation of acridine dyes using anatase and rutile TiO2.

The adsorption and photodegradation of acridine orange (AO) and acriflavine (AF) dyes on two mesoporous titania crystalline phases, anatase and rutile, were experimentally studied. Anatase and rutile were characterized by nitrogen adsorption, electron scanning and transmission microscopy, and X-ray diffraction. The adsorption capacity of rutile was higher than that of anatase, while the reverse is observed for photodegradation of both dyes. The adsorption of AF on both adsorbents was higher than that of AO, which was related with the smaller size of AF molecules compared with those of AO, therefore the access of AF to the adsorption sites is favored.

Enhancing CaP Biomimetic Growth on TiO2 Cuboids Nanoparticles via Highly Reactive Facets

Pure decahedral anatase TiO(2) particles with high content of reactive {001} facets were obtained from titanium(IV) tetrachloride (TiCl(4)) using a microemulsions droplet system at specific conditions as chemical microreactor. The product was systematically characterized by X-ray diffraction, field-emission scanning and transmission electron microscopy (FE-SEM, TEM), N(2) adsorption-desorption isotherms, FT-IR and UV-vis spectroscopy, and photoluminescence studies. The obtained cuboids around 90 nm in size have a uniform and dense surface morphology with a BET specific surface area of 11.91 m(2) g(-1) and a band gap energy (3.18 eV) slightly inferior to the anatase dominated by the less-reactive {101} surface (3.20 eV). The presence of reactive facets on titania anatase favors the biomimetic growth of amorphous tricalcium phosphate after the first day of immersion in simulated human plasma. The results presented here can facilitate and improve the integration of anchored implants and enhance the biological responses to the soft tissues.

Surface phase behavior and domain topography of ascorbyl palmitate monolayers.

Ascorbyl palmitate (ASC(16)) is a molecule of potential pharmacological interest due to its antioxidant properties and amphiphilic nature. The surface behavior of ASC(16) was studied using Langmuir monolayers and Brewster angle microscopy. This molecule formed stable monolayers at room temperature that showed phase transition from a liquid-expanded to liquid-condensed or crystalline phase, depending on the subphase conditions. Using a theoretical approach, we were able to explain the behavior of the ASC(16) film at different bulk pH values and salt conditions based on the surface pH and the dissociation fraction of the film. Both condensed phases corresponded to highly packed conditions with the crystalline phase occurring at a low charge density, showing molecular tilting and preferential growth at characteristic angles, while the liquid-condensed phase formed in highly charged surfaces revealed small flowerlike domains probably as a consequence of internal dipole repulsion. A smaller perpendicular dipole moment was observed for the crystalline than the liquid-condensed phase which may explain the domain features. In conclusion, ASC(16) showed a complex surface behavior that was highly sensitive to subphase conditions.

Bone-repair properties of biodegradable hydroxyapatite nano-rod superstructures

Nano-hydroxyapatite (nano-HAp) materials show an analogous chemical composition to the biogenic mineral components of calcified tissues and depending on their topography they may mimic the specific arrangement of the crystals in bone. In this work, we have evaluated the potential of four synthesized nano-HAp superstructures for the in vitro conditions of bone-repair. Experiments are underway to investigate the effects of the material microstructure, surface roughness and hydrophilicity on their osseo-integration, osteo-conduction and osteo-induction abilities. Materials were tested in the presence of both, rat primary osteoblasts and rabbit mesenchymal stem cells. The following aspects are discussed: (i) cytotoxicity and material degradation; (ii) rat osteoblast spreading, proliferation and differentiation; and (iii) rabbit mesenchymal stem cell adhesion on nano-HAp and nano-HAp/collagen type I coatings. We effectively prepared a material based on biomimetic HAp nano-rods displaying the appropriate surface topography, hydrophilicity and degradation properties to induce the in vitro desired cellular responses for bone bonding and healing. Cells seeded on the selected material readily attached, proliferated and differentiated, as confirmed by cell viability, mitochondrial metabolic activity, alkaline phosphatase (ALP) activity and cytoskeletal integrity analysis by immunofluorescence localization of alpha-smooth muscle actin (α-SMA) protein. These results highlight the influence of materials surface characteristics to determine their tissue regeneration potential and their future use in engineering osteogenic scaffolds for orthopedic implants.

Mimicking Natural Fibrous Structures of Opals by Means of a Microemulsion-Mediated Hydrothermal Method

Silica-based nanomaterials are of great interest because of their potential applications in constructing electronic and optoelectronic nanodevices. Especially significant are those that combine the properties of photonic crystal with a fibrous semiconductor structure. Here we report the use of microemulsion droplet systems as a simple and controllable route for the synthesis of 3D opals materials with an unusual fibrous microstructure similar to those that exist in nature. By this method, we demonstrate the creation of very long fibrils of 30-50 nm diameter and more than 20 μm length showing simultaneous short and long wavelength light emissions and band gap values (5.50 and 4.41 eV) comparable to those obtained for silicon-based metal oxide semiconductors.

Counterion effect on the solution and thermodynamic properties of lithium perfluoroalkanoates

The isotherms of conductivity of lithium perfluorooctanoate and perfluoroundecanoate were measured and the critical micelle concentration, cmc, degree of ionization of the micelles, β, determined in a range of temperatures above the Krafft point. The thermodynamic parameters, Gibbs free energy, , enthalpy , and entropy of micelle formation, were determined from a proposed thermodynamic model. Apparent molar volume and the apparent molar adiabatic compressibility for both surfactants have been calculated over a wide concentration range from density and ultrasound velocity measurements. Positive deviations of the apparent molar volume from the Debye–Hückel limiting law in dilute solutions indicate the existence of premicellar aggregation. Changes in the slope of adiabatic compressibility of lihium perfluoroundecanoate from positive to negative have been interpreted in terms of solute solvent interactions. Dynamic surface tension measurements allow us to calculated diffusion coefficients, areas and aggregation numbers. These values are discussed comparing the corresponding sodium compounds.

Thermodynamic and elastic fluctuation analysis of Langmuir mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB).

The physicochemical and elastic properties of Langmuir mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB) were evaluated. The experiments were performed with a constant surface pressure penetration Langmuir balance based on Axisymmetric Drop Shape Analysis (ADSA). The behavior of such amphiphiles in monolayer was clearly non-ideal and would be seriously influenced by the amount of HDHC molecules present. The presence of bile acid type molecules caused the monolayer be more condensed (A(c) diminution) and the intermolecular attractive interactions be stronger (high epsilon(0) values). This fact would be related to H-bond formation between water and carboxilate and carbonile groups in the cholesteric ring and agreed with the existence of laterally structured microdomains at the monolayer (determined by the analysis of the first virial coefficient, b(0)<1, of the state equation). The miscibility of both surfactants in the monolayer, their high bulk hydrophobicity (pi(c)>35 mJ m(-2)) just with the obtained negative values of the free energy of mixing Delta G(mix), and the excess second virial coefficient (b(1))(E) obtained allows us to infer that net attractive interaction existed between HDHC and DDAB molecules at the monolayer and that mixed systems would be able to be used in the formulation of supramolecular assemblies.

Self-Assembly Drugs: From Micelles to Nanomedicine

Self-assembly has fascinated many scientists over the past few decades. Rapid advances and widespread interest in the study of this subject has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nano- and mesoscopic dimensions. Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries for scientists seeking to design novel molecular materials exhibiting unusual properties, and for researchers investigating the structure and function of biomolecules. Consequently, self-assembly transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field including nanotechnology and nanomedicine. Basically, self-assembly focuses on a wide range of discrete molecules or molecular assemblies and uses physical transformations to achieve its goals. In this Review, we present a comprehensive overview of the advances in the field of drug self-assembly and discuss in detail the synthesis, self-assembly behavior, and physical properties as well as applications. We refer the reader to past reviews dealing with colloidal molecules and colloidal self-assembly. In the first part, we will discuss, compare, and link the various bioinformatic procedures: Molecular Dynamics and Quantitative Structure Activity Relationship. The second section deals with the self-assembly behavior in more detail, in which we focus on several experimental techniques, selected according to the depth of knowledge obtained. The last part will review the advances in drug-protein assembly. Nature provides many examples of proteins that form their substrate binding sites by bringing together the component pieces in a process of self-assembly. We will focus in the understanding of physical properties and applications developing thereof.