Cesar G. Gomez

pH-induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system.

Multilayers of poly(acrylic acid), PAA, and chitosan, CHI, have been built by the layer-by-layer (LbL) method from aqueous solutions at different pH values and analyzed by the dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The results showed that under all of the assembly conditions considered the growth of the films is nonlinear. The thickness of the PAA layers increases as the pH of the assembling solutions decreases, whereas the adsorption of CHI is almost unaffected by the pH conditions. The comparison of the thickness obtained by D-QCM and by ellipsometry has allowed us to calculate the water content of the films, showing that the multilayers are highly hydrated, with an average water content higher than 20%. The analysis of D-QCM data has provided high-frequency values of the complex shear modulus that are in the megapascal range and shows a transition from mainly viscous to mainly elastic behavior for the added PAA layers, depending on the pH. The monomer surface density in each layer (obtained from the combination of ellipsometry and differential refractive index measurements) indicated that the monomer density depends on the assembly conditions. It was found that the adsorption kinetics is a bimodal process, with characteristic times that depend on the number and nature of the layers. Finally, the possibility of using of these multilayers as a drug storage and delivery system has been evaluated.

Effects of experimental variables on the synthesis of porous matrices

Macroporous beads, poly(ethylene glycol dimethacrylate-co-acrylic acid) [poly(EGDMA-co-AAc)], and poly(ethylene glycol dimethacrylate-co-hydroxyethyl methacrylate) [poly(EGDMA-co-HEMA)] were prepared by the suspension polymerization technique in the presence of a porogen agent. Different experimental conditions such as amount of initiator, porogen type, and temperature were studied to optimize the polymerization systems. These hydrophilic copolymers were characterized by IR spectroscopy, scanning electron microscopy, specific surface area, and swelling in water. A new parameter, H, defined as the ratio between the equilibrium weight swelling ratio (q w ) and equilibrium volume swelling ratio (q v ), allowed to select the reaction conditions from which matrices with high capacity of water sorption and low stretching degree were reached.

Recent Studies on Alginates Based Blends, Composites, and Nanocomposites

Alginate is the generic name given to the salts of alginic acids. Alginic acids are polyuronides, i.e., polysaccharides molecules which are built up of uronic acid residues, molecules with a carboxyl group on the carbon that is not part of the ring, Commercial alginates are currently obtained by extraction from brown seaweeds such as Laminaria digitata, Laminaria hyperborea, and Macrocystis pyrifera. However, several bacteria such as the nitrogen-fixing aerobe Azotobacter vinelandii and the opportunistic pathogen Pseudomonas aeruginosa also produce alginate. Alginates are unique in terms of their properties such as emulsifiers, thickeners, stabilizers, gelling and film forming, resulting in several applications for the food and pharmaceutical industries. Alginate has been regarded as an excellent polysachaccharide for gel systems because of its unique features such as biocompatibility, biodegradability, immnogenecity, and non-toxicity. In the biomedical area, alginates have been used as devices in several human health applications, such as excipients in drug delivery (DDS), wound dressings, as dental impression materials and in some formulations preventing gastric reflux, among others. Main characteristics and chemical modification, along with some interesting properties and applications are reviewed along this chapter.

Influence of the morphology of poly(EGDMA-co-HEMA) on the chemical modifications and retention of O-phosphothreonine.

The influence of the morphology of ethylene glycol dimethacrylate-hydroxyethyl methacrylate copolymer [poly(EGDMA-co-HEMA)] base support to obtain different Fe(3+)-containing sorbents and their properties in retention of O-phosphothreonine [Thre(P)] is examined in this paper. Three base supports poly(EGDMA-co-HEMA) (I-III) were obtained using different quantities of initiator in suspension polymerization reactions. These products were submitted to chemical modifications using 1,4-butanediol diglycidyl ether (BDGE) in activation reactions and different chelating agents (iminodiacetic acid, IDA; disodium ethylenediamine tetraacetate, EDTA; and hexamethylenediamine tetrapropanoic acid, HMDTP) in coupling reactions to attain Fe(3+)-containing sorbents. Properties such as specific surface area (S(s)), specific pore volume (V(p)), scanning electron microscopy (SEM), IR spectroscopy, quantity of functional groups (oxirane and carboxyl), amount of chelated metal ion, ligand occupation (L), swelling studies as well as quantity of O-phosphoamino acid retained were used as comparative parameters for matrices. In general, the derivatization reactions proved to be more efficient when higher S(s) of macropores (50-400,000 nm) were available in the matrix. In our case, it was observed when highest percentage of initiator was used. On the other hand, the effect of accessibility of surface area on the yield of coupling reactions was noticed when comparing the different chelating agents since the number of carboxyl groups present in products was higher when the molecular size of the chelating agent was lower. Although all Fe(3+)-containing sorbents resulted efficient to retain Thre(P), the values of retention of the amino acid were slightly higher when IDA-containing matrices were used irrespective of the quantity of metal chelated. This could be probably due to the fact that the IDA ligand could be bounded to the matrix in sites that though accessible for the center of adsorption were hard for Thre(P) to access.

Influence of the polymeric morphology of sorbents on their properties in affinity chromatography.

The influence of the polymeric morphology of different types of Fe(3+)-containing sorbents and their properties in retention of phosphoamino acids is presented in this paper. Poly(hydroxylated polybutadienic-hydroxyethyl methacrylate) [poly(PB-HEMA)] and poly(ethylene glycol dimethacrylate-hydroxyethyl methacrylate) [poly(EGDMA-HEMA)] base supports were submitted to chemical modifications to attain metal ion-containing sorbents. Properties such as specific surface area, pore volume, equilibrium volume swelling ratios, extent of conversion rate of functional groups, amount of chelated metal ion, ligand occupation, as well as quantity of phosphoamino acid retained, were used as comparative parameters for those different base matrices. Results suggest that Fe(3+) immobilized on poly(EGDMA-HEMA) base support are more efficient as a group-specific sorbent to retain phosphoamino acids than those obtained using poly(PB-HEMA) base support.

Evaporation Kinetics in Swollen Porous Polymeric Networks

NMR is a fast, nondestructive, and noninvasive technique that can provide information about the pore structure of macroporous polymer beads and the dynamics of liquids confined in them. In this work, we describe the study of the pore structure of the macroporous polymer of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] in the dry but also in the swollen state by measuring relaxation times of liquids contained in the polymer network. The results show that the pore architecture differs from the dry to the soaked state. The behavior of polar liquids during evaporation and deswelling dynamics is monitored and described. An internal migration of water from the swollen polymer mesh into expanding pores takes place. With this procedure it is possible to obtain information about the microscopic morphology behavior of the matrix during evaporation and deswelling. This information is of great interest with the aspect of possible and future applications for these types of materials.

Enhanced Surface Interaction of Water Confined in Hierarchical Porous Polymers Induced by Hydrogen Bonding

Hierarchical porous polymer systems are increasingly applied to catalysis, bioengineering, or separation technology because of the versatility provided by the connection of mesopores with percolating macroporous structures. Nuclear magnetic resonance (NMR) is a suitable technique for the study of such systems as it can detect signals stemming from the confined liquid and translate this information into pore size, molecular mobility, and liquid-surface interactions. We focus on the properties of water confined in macroporous polymers of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate [poly(EGDMA-co-HEMA)] with different amounts of cross-linkers, in which a substantial variation of hydroxyl groups is achieved. As soft polymer scaffolds may swell upon saturation with determined liquids, the use of NMR is particularly important as it measures the system in its operational state. This study combines different NMR techniques to obtain information on surface interactions of water with hydrophilic polymer chains. A transition from a surface-induced relaxation in which relaxivity depends on the pore size to a regime where the organic pore surface strongly restricts water diffusion is observed. Surface affinities are defined through the molecular residence times near the network surface.

Spatially Resolved Monitoring of Drying of Hierarchical Porous Organic Networks

Evaporation kinetics of water confined in hierarchal polymeric porous media is studied by low field nuclear magnetic resonance (NMR). Systems synthesized with various degrees of cross-linker density render networks with similar pore sizes but different response when soaked with water. Polymeric networks with low percentage of cross-linker can undergo swelling, which affects the porosity as well as the drying kinetics. The drying process is monitored macroscopically by single-sided NMR, with spatial resolution of 100 μm, while microscopic information is obtained by measurements of spin-spin relaxation times (T2). Transition from a funicular to a pendular regime, where hydraulic connectivity is lost and the capillary flow cannot compensate for the surface evaporation, can be observed from inspection of the water content in different sample layers. Relaxation measurements indicate that even when the larger pore structures are depleted of water, capillary flow occurs through smaller voids.

Poly(Propylene)-based Films Modified with a Tetracationic Phthalocyanine with Applications in Photodynamic Inactivation of Candida Albicans

ABSTRACT Photoactive films based on polymer-like poly(propylene) were generated and utilized as support of zinc(II)tetramethyltetrapyridino[2,3-b:2′,3′-g:2″,3″-l:2″′,3″′-q]porphyrazinium salt (ZnTM2,3PyPz). Using a photograft polymerization of acrylic acid, the poly(propylene) film was functionalized with carboxyl groups (PP-g-PAAc), which attached ZnTM2,3PyPz by electrostatic bond to form PP-g-PAAc-Pc films. In vitro investigations indicated that PP-g-PAAc-Pc films produced photodynamic inactivation of Candida albicans cells, mainly mediated by a contribution of type II process. According to the results, the photodynamic activity produced by the PP-g-PAAc-Pc film and visible light irradiation can successfully inactivate C. albicans deposited on the surface of the films. GRAPHICAL ABSTRACT