RESUMO

The degradation of mesoporous silica nanoparticles (MSNs) in the biological milieu due to silica hydrolysis plays a fundamental role for the delivery of encapsulated drugs and therapeutics. However, little is known on the evolution of the pore arrangement in the MSNs in biologically relevant conditions. Small Angle X-ray scattering (SAXS) studies were performed on unmodified and PEGylated MSNs with a MCM-48 pore structure and average sizes of 140 nm, exposed to simulated body fluid solution (SBF) at pH 7.4 for different time intervals from 30 min to 24 h. Experiments were performed with silica concentrations below, at and over 0.14 mg/mL, the saturation concentration of silica in water at physiological temperature. At silica concentrations of 1 mg/mL (oversaturation), unmodified MSNs show variation in interpore distances over 6 h exposure to SBF, remaining constant thereafter. A decrease in radius of gyration is observed over the same time. Mesoporosity and radius of gyration of unmodified MSNs remain then unchanged up to 24 h. PEGylated MSNs at 1 mg/mL concentration show a broader diffraction peak but no change in the position of the peak is observed following 24 h exposure to SBF. PEGylated MSNs at 0.01 mg/mL show no diffraction peaks already after 30 min exposure to SBF, while at 0.14 mg/mL a small diffraction peak is present after 30 min exposure but disappears after 1 h.

RESUMO

In this work, monodisperse silica-coated gold nanoparticles (NPs) were synthesized and used for obtaining aqueous colloidal dispersions with an optimum relationship between colloidal stability and photothermal activity. The idea behind this design was to produce systems with the advantages of the presence of a silica shell (biocompatibility, potential for surface modification, and protecting effect) with a minimal loss of optical and thermal properties. With this aim, the photothermal properties of NPs with silica shells of different thicknesses were analyzed under conditions of high radiation extinction. By using amorphous, gel-like silica coatings, thicknesses higher than 40 nm could be obtained without an important loss of the light absorption capacity of the colloids and with a significant photothermal response even at low NP concentrations. The effects produced by changes in the solvent and in the NP concentration were also analyzed. The results show that the characteristics of the shell control both, the photothermal effect and the optical properties of the colloidal dispersions. As the presence of a silica shell strongly enhances the possibilities of adding cargo molecules or probes, these colloids can be considered of high interest for biomedical therapies, sensing applications, remote actuation, and other technological applications.

Assuntos

Nanopartículas Metálicas , Nanoconchas , Coloides/química , Ouro/química , Nanopartículas Metálicas/química , Dióxido de Silício/química , Suspensões

RESUMO

In this work, we describe the preparation and characterization of highly magnetizable chloromethylated polystyrene-based nanocomposite beads. For synthesis optimization, acid-resistant core-shelled maghemite (γ-Fe2O3) nanoparticles are coated with sodium oleate and directly incorporated into the organic medium during a suspension polymerization process. A crosslinking agent, ethylene glycol dimethacrylate, is used for copolymerization with 4-vinylbenzyl chloride to increase the resistance of the microbeads against leaching. X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and optical microscopy are used for bead characterization. The beads form a magnetic composite consisting of ∼500 nm-sized crosslinked polymeric microspheres, embedding ∼8 nm γ-Fe2O3 nanoparticles. This nanocomposite shows large room temperature magnetization (∼24 emu/g) due to the high content of maghemite (∼45 wt %) and resistance against leaching even in acidic media. Moreover, the presence of superficial chloromethyl groups is probed by Fourier transform infrared and X-ray photoelectron spectroscopy. The nanocomposite beads displaying chloromethyl groups can be used to selectively remove aminated compounds that are adsorbed on the beads, as is shown here for the molecular separation of 4-aminobenzoic acid from a mixture with benzoic acid. The high magnetization of the composite beads makes them suitable for in situ molecular separations in environmental and biological applications.

RESUMO

Interfacial supramolecular architectures displaying mesoscale organized components are of fundamental importance for developing materials with novel or optimized properties. Nevertheless, engineering the multilayer assembly of different building blocks onto a surface and exerting control over the internal mesostructure of the resulting film is still a challenging task in materials science. In the present work we demonstrate that the integration of surfactants (as mesogenic agents) into layer-by-layer (LbL) assembled polyelectrolyte multilayers offers a straightforward approach to control the internal film organization at the mesoscale level. The mesostructure of films constituted of hexadecyltrimethylammonium bromide, CTAB, and polyacrylic acid, PAA (of different molecular weights), was characterized as a function of the number of assembled layers. Structural characterization of the multilayered films by grazing-incidence small-angle X-ray scattering (GISAXS), showed the formation of mesostructured composite polyelectrolyte assemblies. Interestingly, the (PAA/CTA)n assemblies prepared with low PAA molecular weight presented different mesostructural regimes which were dependent on the number of assembled layers: a lamellar mesophase for the first bilayers, and a hexagonal circular mesophase for n ≥ 7. This interesting observation was explained in terms of the strong interaction between the substrate and the first layers leading to a particular mesophase. As the film increases its thickness, the prevalence of this strong interaction decreases and the supramolecular architecture exhibits a "bulk" mesophase. Finally, we demonstrated that the molecular weight of the polyelectrolyte has a considerable impact on the meso-organization for the (PAA/CTA)n assemblies. We consider that these studies open a path to new rational methodologies to construct "nanoarchitectured" polyelectrolyte multilayers.

RESUMO

Metal phthalocyanines are promising components in photodynamic therapy. Aluminum phthalocyanine chloride (AlClPc) has been used to treat oral cancer in mice, human carious tissue, lung cancer cells and other conditions. To overcome the high hydrophobicity of AlClPc, phthalocyanine is often encapsulated in nanoformulations. Despite increased usage, little is known about the pharmacokinetics and biodistribution of AlClPc. The aim of this study was the development and validation of a UHPLC-MS method for the determination of AlClPc in solution after extraction from nanoformulations and biological matrices such as plasma and tissue. The described method has been assayed as to selectivity, linearity, limits of detection and quantification, precision and recovery. The present study is the first to describe the behavior of AlClPc in biological matrices with mass spectrometry as well as the first to describe the chromatographic behavior of AlClPc contaminants. Molecular mass analysis identified dechlorination of AlClPc by both LC/MS and MALDI-MS and an adduct formation in LC/MS. The parameters observed indicated that the method has applicability and robustness for use in biodistribution studies.

Assuntos

Cromatografia Líquida de Alta Pressão/normas , Indóis/sangue , Nanoestruturas/química , Compostos Organometálicos/sangue , Fármacos Fotossensibilizantes/sangue , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/normas , Animais , Disponibilidade Biológica , Biotransformação , Óleo de Rícino/química , Sistemas de Liberação de Medicamentos , Emulsões , Humanos , Interações Hidrofóbicas e Hidrofílicas , Indóis/farmacocinética , Indóis/farmacologia , Rim/efeitos dos fármacos , Rim/metabolismo , Limite de Detecção , Fígado/efeitos dos fármacos , Fígado/metabolismo , Pulmão/efeitos dos fármacos , Pulmão/metabolismo , Camundongos , Camundongos Endogâmicos BALB C , Nanoestruturas/administração & dosagem , Compostos Organometálicos/farmacocinética , Compostos Organometálicos/farmacologia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacocinética , Fármacos Fotossensibilizantes/farmacologia , Polietilenoglicóis/química , Baço/efeitos dos fármacos , Baço/metabolismo , Distribuição Tecidual

RESUMO

The development of antifouling coatings with restricted cell and bacteria adherence is fundamental for many biomedical applications. A strategy for the fabrication of antifouling coatings based on the layer-by-layer assembly and thermal annealing is presented. Polyelectrolyte multilayers (PEMs) assembled from chitosan and hyaluronic acid were thermally annealed in an oven at 37°C for 72h. The effect of annealing on the PEM properties and topography was studied by atomic force microscopy, ζ-potential, circular dichroism and contact angle measurements. Cell adherence on PEMs before and after annealing was evaluated by measuring the cell spreading area and aspect ratio for the A549 epithelial, BHK kidney fibroblast, C2C12 myoblast and MC-3T3-E1 osteoblast cell lines. Chitosan/hyaluronic acid PEMs show a low cell adherence that decreases with the thermal annealing, as observed from the reduction in the average cell spreading area and more rounded cell morphology. The adhesion of S. aureus (Gram-positive) and E. coli (Gram-negative) bacteria strains was quantified by optical microscopy, counting the number of colony-forming units and measuring the light scattering of bacteria suspension after detachment from the PEM surface. A 20% decrease in bacteria adhesion was selectively observed in the S. aureus strain after annealing. The changes in mammalian cell and bacteria adhesion correlate with the changes in topography of the chitosan/hyaluronic PEMs from a rough fibrillar 3D structure to a smoother and planar surface after thermal annealing.

Assuntos

Quitosana/química , Animais , Aderência Bacteriana , Escherichia coli , Ácido Hialurônico , Polieletrólitos , Staphylococcus aureus , Propriedades de Superfície

RESUMO

The layer-by-layer assembly of polyelectrolyte multilayers (PEMs) from natural or synthetic polyelectrolytes constitutes a very versatile and simple strategy to modify surfaces and modulate cell behavior. PEMs assembled from natural polyelectrolytes are very appealing for biological and medical applications due to their high biocompatibility. However, PEMs from natural polyelectrolytes display poor cell adhesion as they are soft materials with an elasticity modulus of a few kilopascal. In this report, the authors present results on the modulation of cell adhesion of different immortalized cell lines by PEMs. Two strategies are employed to vary cell adhesion: (1) a heterogeneous polyelectrolyte multilayer is assembled employing a rigid bottom block including a synthetic polyelectrolyte with a soft upper block of natural polyelectrolytes and (2) polyelectrolyte multilayers from natural polyelectrolytes are thermally annealed after assembly. The physicochemical characteristics of the PEMs change upon thermal treatment. Depending on the composition of the polyelectrolyte multilayer, cell adhesion may be enhanced or reduced. Based on the impact on PEM properties and cell adhesion caused by thermal annealing, a temperature gradient is applied to a PEM of poly-l-lysine/alginate to induce a spatial variation of PEM properties, resulting in a gradient in cell adhesion. The strategies shown here can be employed as simple alternatives to tailor PEM properties by means of fully biocompatible procedures.

Assuntos

Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/metabolismo , Adesão Celular , Polieletrólitos/síntese química , Polieletrólitos/metabolismo , Propriedades de Superfície , Células A549 , Fenômenos Químicos , Células Epiteliais/fisiologia , Humanos

RESUMO

The search for strategies to improve the performance of bioelectrochemical platforms based on supramolecular materials has received increasing attention within the materials science community, where the main objective is to develop low-cost and flexible routes using self-assembly as a key enabling process. Important contributions to the performance of such bioelectrochemical devices have been made based on the integration and supramolecular organization of redox-active polyelectrolyte-surfactant complexes on electrode supports. Here, we examine the influence of the processing solvent on the interplay between the supramolecular mesoorganization and the bioelectrochemical properties of redox-active self-assembled nanoparticle-polyelectrolyte-surfactant nanocomposite thin films. Our studies reveal that the solvent used in processing the supramolecular films and the presence of metal nanoparticles not only have a substantial influence in determining the mesoscale organization and morphological characteristics of the film but also have a strong influence on the efficiency and performance of the bioelectrochemical system. In particular, a higher bioelectrochemical response is observed when nanocomposite supramolecular films were cast from aqueous solutions. These observations seem to be associated with the fact that the use of aqueous solvents increases the hydrophilicity of the film, thus favoring the access of glucose, particularly at low concentrations. We believe that these results improve our current understanding of supramolecular nanocomposite materials generated via polyelectrolyte-surfactant complexes, in order to use the processing conditions as a variable to improve the performance of bioelectrochemical devices.

Assuntos

Tensoativos/química , Glucose Oxidase , Oxirredução , Polieletrólitos , Solventes

RESUMO

Polyelectrolyte multilayers (PEMs) with different polycation/polyanion pairs are fabricated by the layer-by-layer technique employing synthetic, natural, and both types of polyelectrolytes. The impact of the chemical composition of PEMs on cell adhesion is assessed by studying cell shape, spreading area, focal contacts, and cell proliferation for the A549 cell line. Cells exhibit good adhesion on PEMs containing natural polycations and poly(sodium 4-styrenesulfonate) (PSS) as polyanion, but limited adhesion is observed on PEMs fabricated from both natural polyelectrolytes. PEMs are then assembled, depositing a block of natural polyelectrolytes on top of a stiffer block with PSS as polyanion. Cell adhesion is enhanced on top of the diblock PEMs compared to purely natural PEMs. This fact could be explained by the interdigitation between polyelectrolytes from the two blocks. Diblock PEM assembly provides a simple means to tune cell adhesion on biocompatible PEMs.

Assuntos

Adesão Celular/efeitos dos fármacos , Polietilenos/farmacologia , Polilisina/farmacologia , Polímeros/farmacologia , Compostos de Amônio Quaternário/farmacologia , Ácidos Sulfônicos/farmacologia , Células A549 , Resinas Acrílicas/química , Resinas Acrílicas/farmacologia , Proliferação de Células/efeitos dos fármacos , Forma Celular/efeitos dos fármacos , Forma Celular/fisiologia , Sobrevivência Celular/efeitos dos fármacos , Adesões Focais/efeitos dos fármacos , Adesões Focais/fisiologia , Humanos , Polietilenoimina/química , Polietilenoimina/farmacologia , Polietilenos/química , Polilisina/química , Polímeros/química , Compostos de Amônio Quaternário/química , Relação Estrutura-Atividade , Ácidos Sulfônicos/química , Propriedades de Superfície

RESUMO

Hybrid polyelectrolyte multilayer systems were fabricated on top of planar surfaces and colloidal particles via layer by layer (LbL) assembly of polystyrene sulphonate (PSS) and polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) polymersomes. Polymersomes were prepared by self assembly of PBzMA-b-PDMAEMA copolymer, synthesised by group transfer polymerisation. Polymersomes display a diameter of 270 nm and a shell thickness of 11nm. Assembly on planar surfaces was followed by means of the Quartz Crystal Microbalance with Dissipation (QCM-D) and Atomic Force Microscopy (AFM). Detailed information on the assembly mechanism and surface topology of the polymersome/polyelectrolyte films was thereby obtained. The assembly of polymersomes and PSS on top of silica particles of 500 nm in diameter was confirmed by ζ-potential measurements. Confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that polymersome/PSS coated silica particles increase in total diameter up to 3-5µm. This hints toward the formation of densely packed polymersome layers. In addition, CLSM showed that polymersome/PSS films exhibit a high loading capacity that could potentially be used for encapsulation and delivery of diverse chemical species. These results provide an insight into the formation of multilayered films with compartmentalised hydrophilic/hydrophobic domains and may lead to the successful application of polymersomes in surface-engineered colloidal systems.

Assuntos

Coloides/química , Eletrólitos/química , Polímeros/química , Microscopia/métodos , Tamanho da Partícula

RESUMO

Silver nanoparticles have been functionalized in situ with the electrically conducting polymer, poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) via colloidal synthesis. The formation of the functionalized silver nanoparticles, hereafter designated Ag(PEDOT:PSS), was confirmed by the appearance of the characteristic plasmon absorption peak at 420 nm in the UV-Vis spectrum of the aqueous suspension and by TEM analysis, where spherical particles with a mean size of around 8 nm (metallic core) were observed. Homogeneous thin films with granular topography, as observed by AFM, were prepared by self assembly. Electrical studies of the films showed an increase in electrical conductivity of three orders of magnitude with respect to the polymer film presumably due to the presence of the silver core. The conductive polymer/silver composite films also exhibit interesting electrochromic switching between blue and brown. These properties suggest the possibility of a variety of applications of Ag(PEDOT:PSS) films such as in electro optics devices, smart windows, amperometric sensors and capacitors.