Layer-by-layer Thin Films Of Alginate/chitosan And Hyaluronic Acid/chitosan With Tunable Thickness And Surface Roughness

Layer-by-layer (LbL) is a bottom-up technique used for construction of films with selfassembly and self-organizing properties. In most cases, the fundamental driving force for the formation of these films is originated from the electrostatic interaction between oppositely charged species. The charged segments of polyelectrolytes behave as small building units and their orientation and position can be designed to target structures of great complexity. Furthermore, the technique enables the use of various materials, including natural polymers. In this work, we chose the cationic biopolymer chitosan (CHI) and the negative polyelectrolytes sodium alginate (ALG) and hyaluronic acid (HA). The aim of this study was to evaluate the effect of ionic strength (0 versus 200 mM) and pH (3 versus 5) on ALG/CHI and HA/CHI nanostructured multilayered thin films properties. From profilometry and atomic force microscopy (AFM) analyses, changes in thickness and roughness of the coatings were monitored. The presence of salt in polyelectrolyte solutions induced the polymer chains to adopt conformations with more loops and tails and this arrangement in solution was transmitted to films, resulting in rougher surfaces. Furthermore, the film thickness can be precisely controlled by adjusting the pH of the polyelectrolyte solution. The variation of these parameters shows that it is possible to molecularly control chemical and structural properties of nanostructured coatings, thus opening up new possibilities of application (e.g. cell adhesion). © (2014) Trans Tech Publications, Switzerland.783-78612261231CDMM,Dynamic systems Inc.,et al,National Science Foundataion (NSF),Office of Naval Research (ONR),POSCODecher, G., Nanoassemblies, F., Toward Layered Polymeric Multicomposites (1997) Science, 277, pp. 1232-1237Voigt, U., Jaeger, W., Findenegg, G.H., Klitzing, R.V., Charge Effects on the Formation of Multilayers Containing Strong Polyelectrolytes (2003) The Journal of Physical Chemistry B, 107, pp. 5273-5280Delcea, M., Möhwald, H., Skirtach, A.G., Stimuli-responsive LbL capsules and nanoshells for drug delivery (2011) Advanced Drug Delivery Reviews, 63, pp. 730-747Vasconcellos, F.C., Swiston, A.J., Beppu, M.M., Cohen, R.E., Rubner, M.F., Bioactive Polyelectrolyte Multilayers: Hyaluronic Acid Mediated B Lymphocyte Adhesion (2010) Biomacromolecules, 11, pp. 2407-2414Etienne, O., Gasnier, C., Taddei, C., Voegel, J.-C., Aunis, D., Schaaf, P., Metz-Boutigue, M.-H., Egles, C., Antifungal coating by biofunctionalized polyelectrolyte multilayered films (2005) Biomaterials, 26, pp. 6704-6712Lichter, J.A., van Vliet, K.J., Rubner, M.F., Design of Antibacterial Surfaces and Interfaces: Polyelectrolyte Multilayers as a Multifunctional Platform (2009) Macromolecules, 42, pp. 8573-8586Tsuge, Y., Kim, J., Sone, Y., Kuwaki, O., Shiratori, S., Fabrication of transparent TiO2 film with high adhesion by using self-assembly methods: Application to super-hydrophilic film (2008) Thin Solid Films, 516, pp. 2463-2468Richert, L., Lavalle, P., Payan, E., Shu, X., Prestwich, G., Stoltz, J., Schaaf, P., Picart, C., Layer by layer buildup of polysaccharide films: Physical chemistry and cellular adhesion aspects (2004) Langmuir, 20, pp. 448-458Rinaudo, M., Main properties and current applications of some polysaccharides as biomaterials (2008) Polymer International, 57, pp. 397-430Alves, N.M., Picart, C., Mano, J.F., Self Assembling and Crosslinking of Polyelectrolyte Multilayer Films of Chitosan and Alginate Studied by QCM and IR Spectroscopy (2009) Macromolecular Bioscience, 9, pp. 776-785Jin, R.-H., Yuan, J.-J., Biomimetically Controlled Formation of Nanotextured Silica/Titania Films on Arbitrary Substrates and Their Tunable Surface Function (2009) Advanced Materials, 21, pp. 3750-3753Lavalle, P., Gergely, C., Cuisinier, F.J.G., Decher, G., Schaaf, P., Voegel, J.C., Picart, C., Comparison of the Structure of Polyelectrolyte Multilayer Films Exhibiting a Linear and an Exponential Growth Regime: An in Situ Atomic Force Microscopy Study (2002) Macromolecules, 35, pp. 4458-4465Box, G.E.P., Hunter, W.G., Hunter, J.S., (1978) Statistics For Experimenters: An Introduction to Design, Data Analysis, , and model building, WileyShiratori, S.S., Rubner, M.F., PH-Dependent Thickness Behavior of Sequentially Adsorbed Layers of Weak Polyelectrolytes (2000) Macromolecules, 33, pp. 4213-4219Ikeda, A., Takemura, A., Ono, H., Preparation of low-molecular weight alginic acid by acid hydrolysis (2000) Carbohydrate Polymers, 42, pp. 421-425Voigt, U., Khrenov, V., Thuer, K., Hahn, M., Jaeger, W., von Klitzing, R., The effect of polymer charge density and charge distribution on the formation of multilayers (2003) Journal of Physics- Condensed Matter, 15, pp. S213-S218Dubas, S.T., Schlenoff, J.B., Polyelectrolyte Multilayers Containing a Weak Polyacid: Construction and Deconstruction (2001) Macromolecules, 34, pp. 3736-3740Rojas, O.J., Claesson, P.M., Muller, D., Neuman, R.D., The Effect of Salt Concentration on Adsorption of Low-Charge-Density Polyelectrolytes and Interactions between Polyelectrolyte- Coated Surfaces (1998) Journal of Colloid and Interface Science, 205, pp. 77-88McAloney, R.A., Sinyor, M., Dudnik, V., Goh, M.C., Atomic Force Microscopy Studies of Salt Effects on Polyelectrolyte Multilayer Film Morphology (2001) Langmuir, 17, pp. 6655-6663Ren, K., Wang, Y., Ji, J., Lin, Q., Shen, J., Construction and deconstruction of PLL/DNA multilayered films for DNA delivery: Effect of ionic strength (2005) Colloids and Surfaces B: Biointerfaces, 46, pp. 63-69Bohmer, M.R., Evers, O.A., Scheutjens, J.M.H.M., Weak polyelectrolytes between two surfaces: Adsorption and stabilization (1990) Macromolecules, 23, pp. 2288-2301Fery, A., Schöler, B., Cassagneau, T., Caruso, F., Nanoporous Thin Films Formed by Salt- Induced Structural Changes in Multilayers of Poly(acrylic acid) and Poly(allylamine) (2001) Langmuir, 17, pp. 3779-378

Surface Modification Of Polyelectrolyte Multilayers By High Radio Frequency Air Plasma Treatment

Low-temperature plasma treatments are used to perform surface modification on polymers, aiming to improve the surface properties according to the desired application. In this work, polyelectrolyte multilayers (PEMs), built by layer-by-layer deposition technique, were treated using high frequency low-temperature air plasma. We evaluated the effect of the exposure time (20 and 300 s) and its effects on PEMs with two different top layers: alginate and carboxymethylcellulose. Chitosan was used as the cationic polymer to build the LbL films with the oppositely charged anionic polymers, alginate and carboxymethylcellulose. Our results showed that the surface topology, wettability and free charges within layers are highly correlated to the polymer pair used. PEMs of the chitosan/alginate system are thinner and hydrophilic, and present a surface with wider peaks. We found that plasma treatment promotes substantial changes on the PEMs and that 20 s of exposure time is enough to perform these changes. In all cases, after plasma treatment, PEMs' thickness and free charge distribution were reduced and wettability was enhanced.329287291Decher, G., Fuzzy nanoassemblies toward layered polymeric multicomposites (1997) Science, 277, pp. 1232-1237Decher, G., Hong, J.D., Schmitt, J., Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces (1992) Thin Solid Films, 210-211, pp. 831-835De Villiers, M.M., Otto, D.P., Strydom, S.J., Lvov, Y.M., Introduction to nanocoatings produced by layer-by-layer (LbL) self-assembly (2011) Adv. Drug Delivery Rev., 63, pp. 701-715Goddard, J.M., Hotchkiss, J.H., Polymer surface modification for the attachment of bioactive compounds (2007) Prog. Polym. Sci., 32, pp. 698-725Gil'Man, A.B., Low-temperature plasma treatment as an effective method for surface modification of polymeric materials (2003) High Energy Chem., 37, pp. 17-23Bormashenko, E., Chaniel, G., Grynyov, R., Towards understanding hydrophobic recovery of plasma treated polymers: Storing in high polarity liquids suppresses hydrophobic recovery (2013) Appl. Surf. Sci., 273, pp. 549-553Pantoja, M., Encinas, N., Abenojar, J., Martínez, M.A., Effect of tetraethoxysilane coating on the improvement of plasma treated polypropylene adhesion (2013) Appl. Surf. Sci., 280, pp. 850-857Safinia, L., Wilson, K., Mantalaris, A., Bismarck, A., Atmospheric plasma treatment of porous polymer constructs for tissue engineering applications (2007) Macromol. Biosci., 7, pp. 315-327Tompkins, B.D., Dennison, J.M., Fisher, E.R., H2O plasma modification of track-etched polymer membranes for increased wettability and improved performance (2013) J. Membr. Sci., 428, pp. 576-588Tsougeni, K., Petrou, P.S., Tserepi, A., Kakabakos, S.E., Gogolides, E., Nano-texturing of poly(methyl methacrylate) polymer using plasma processes and applications in wetting control and protein adsorption (2009) Microelectron. Eng., 86, pp. 1424-1427Riccardi, C., Barni, R., Selli, E., Mazzone, G., Massafra, M.R., Marcandalli, B., Poletti, G., Surface modification of poly(ethylene terephthalate) fibers induced by radio frequency air plasma treatment (2003) Appl. Surf. Sci., 211, pp. 386-397Zhang, C., Zhou, Y., Shao, T., Xie, Q., Xu, J., Yang, W., Hydrophobic treatment on polymethylmethacrylate surface by nanosecond-pulse DBDs in CF4 at atmospheric pressure (2014) Appl. Surf. Sci., 311, pp. 468-477Shao, T., Zhang, C., Long, K., Zhang, D., Wang, J., Yan, P., Zhou, Y., Surface modification of polyimide films using unipolar nanosecond-pulse DBD in atmospheric air (2010) Appl. Surf. Sci., 256, pp. 3888-3894Shao, T., Zhang, C., Yu, Y., Niu, Z., Jiang, H., Xu, J., Li, W., Zhou, Y., Discharge characteristic of nanosecond-pulse DBD in atmospheric air using magnetic compression pulsed power generator (2012) Vacuum, 86, pp. 876-880Niu, Z., Zhang, C., Shao, T., Fang, Z., Yu, Y., Yan, P., Repetitive nanosecond-pulse dielectric barrier discharge and its application on surface modification of polymers (2013) Surf. Coat. Technol., 228, pp. S578-S582Rinaudo, M., Pavlov, G., Desbrières, J., Influence of acetic acid concentration on the solubilization of chitosan (1999) Polymer, 40, pp. 7029-7032Martinsen, A., Storrø, I., Skjårk-Bræk, G., Alginate as immobilization material: III. Diffusional properties (1992) Biotechnol. Bioeng., 39, pp. 186-194Biesheuvel, P.M., Cohen Stuart, M.A., Electrostatic free energy of weakly charged macromolecules in solution and intermacromolecular complexes consisting of oppositely charged polymers (2004) Langmuir, 20, pp. 2785-2791Vasconcellos, F.C., Swiston, A.J., Beppu, M.M., Cohen, R.E., Rubner, M.F., Bioactive polyelectrolyte multilayers: Hyaluronic acid mediated B lymphocyte adhesion (2010) Biomacromolecules, 11, pp. 2407-2414Haberska, K., Ruzgas, T., Polymer multilayer film formation studied by in situ ellipsometry and electrochemistry (2009) Bioelectrochemistry, 76, pp. 153-161Radeva, T., Kamburova, K., Petkanchin, I., Formation of polyelectrolyte multilayers from polysaccharides at low ionic strength (2006) J. Colloid Interface Sci., 298, pp. 59-65Vesel, A., Modification of polystyrene with a highly reactive cold oxygen plasma (2010) Surf. Coat. Technol., 205, pp. 490-497Ozgen, O., Aksoy, E.A., Hasirci, V., Hasirci, N., Surface characterization and radical decay studies of oxygen plasma-treated PMMA films (2013) Surf. Interface Anal., 45, pp. 844-853Berger, F.M., Ludwig, B.J., Wielich, K.H., The hydrophilic and acid binding properties of alginates (1953) Am. J. Dig. Dis., 20, pp. 39-42Ikeda, A., Takemura, A., Ono, H., Preparation of low-molecular weight alginic acid by acid hydrolysis (2000) Carbohydr. Polym., 42, pp. 421-425Slepička, P., Kasálková, N.S., Stránská, E., Bačáková, L., Švorčík, V., Surface characterization of plasma treated polymers for applications as biocompatible carriers (2013) Express Polym. Lett., 7, pp. 535-545Geyter, N., Sarani, A., Jacobs, T., Nikiforov, A.Y., Desmet, T., Dubruel, P., Surface modification of poly-(-caprolactone with an atmospheric pressure plasma jet (2013) Plasma Chem. Plasma Process., 33, pp. 165-175Gołda, M., Brzychczy-Włoch, M., Faryna, M., Engvall, K., Kotarba, A., Oxygen plasma functionalization of parylene C coating for implants surface: Nanotopography and active sites for drug anchoring (2013) Mat. Sci. Eng. C-Bio S, 33, pp. 4221-4227Borges, A.M.G., Benetoli, L.O., Licínio, M.A., Zoldan, V.C., Santos-Silva, M.C., Assreuy, J., Pasa, A.A., Soldi, V., Polymer films with surfaces unmodified and modified by non-thermal plasma as new substrates for cell adhesion (2013) Mat. Sci. Eng. C-Bio S, 33, pp. 1315-1324Kamińska, A., Kaczmarek, H., Kowalonek, J., The influence of side groups and polarity of polymers on the kind and effectiveness of their surface modification by air plasma action (2002) Eur. Polym. J., 38, pp. 1915-1919Chung, A.J., Rubner, M.F., Methods of loading and releasing low molecular weight cationic molecules in weak polyelectrolyte multilayer films (2002) Langmuir, 18, pp. 1176-1183Yamanlar, S., Sant, S., Boudou, T., Picart, C., Khademhosseini, A., Surface functionalization of hyaluronic acid hydrogels by polyelectrolyte multilayer films (2011) Biomaterials, 32, pp. 5590-5599Yoo, D., Shiratori, S.S., Rubner, M.F., Controlling bilayer composition and surface wettability of sequentially adsorbed multilayers of weak polyelectrolytes (1998) Macromolecules, 31, pp. 4309-4318Sakaguchi, H., Serizawa, T., Akashi, M., Layer-by-layer assembly on hydrogel surfaces and control of human whole blood coagulation (2003) Chem. Lett., 32, pp. 174-175Mendelsohn, J.D., Yang, S.Y., Hiller, J.A., Hochbaum, A.I., Rubner, M.F., Rational design of cytophilic and cytophobic polyelectrolyte multilayer thin films (2002) Biomacromolecules, 4, pp. 96-10

Removal Of Glyphosate Herbicide From Water Using Biopolymer Membranes

Enormous amounts of pesticides are manufactured and used worldwide, some of which reach soils and aquatic systems. Glyphosate is a non-selective herbicide that is effective against all types of weeds and has been used for many years. It can therefore be found as a contaminant in water, and procedures are required for its removal. This work investigates the use of biopolymeric membranes prepared with chitosan (CS), alginate (AG), and a chitosan/alginate combination (CS/AG) for the adsorption of glyphosate present in water samples. The adsorption of glyphosate by the different membranes was investigated using the pseudo-first order and pseudo-second order kinetic models, as well as the Langmuir and Freundlich isotherm models. The membranes were characterized regarding membrane solubility, swelling, mechanical, chemical and morphological properties. The results of kinetics experiments showed that adsorption equilibrium was reached within 4h and that the CS membrane presented the best adsorption (10.88mg of glyphosate/g of membrane), followed by the CS/AG bilayer (8.70mg of glyphosate/g of membrane). The AG membrane did not show any adsorption capacity for this herbicide. The pseudo-second order model provided good fits to the glyphosate adsorption data on CS and CS/AG membranes, with high correlation coefficient values. Glyphosate adsorption by the membranes could be fitted by the Freundlich isotherm model. There was a high affinity between glyphosate and the CS membrane and moderate affinity in the case of the CS/AG membrane. Physico-chemical characterization of the membranes showed low values of solubility in water, indicating that the membranes are stable and not soluble in water. The SEM and AFM analysis showed evidence of the presence of glyphosate on CS membranes and on chitosan face on CS/AG membranes. The results showed that the glyphosate herbicide can be adsorbed by chitosan membranes and the proposed membrane-based methodology was successfully used to treat a water sample contaminated with glyphosate. Biopolymer membranes therefore potentially offer a versatile method to eliminate agricultural chemicals from water supplies.151353360Adamson, A.W., (1976) Physical Chemistry of Surfaces, p. 300. , John Wiley &Sons, New YorkAouada, F.A., Moura, M.R., Orts, W.J., Mattoso, L.H.C., Polyacrylamide and methylcellulose hydrogel as delivery vehicle for the controlled release of paraquat pesticide (2010) J.Mater. Sci., 45, pp. 4977-4985Bhaskara, B.L., Nagaraja, P., Direct sensitive spectrophotometric determination of glyphosate by using ninhydrin as a chromogenic reagent in formulations and environmental water samples (2006) Helvetica Chim. Acta, 89, pp. 2686-2693Chen, F.-X., Zhou, C.R., Li, G.P., Peng, F.F., Thermodynamics and kinetics of glyphosate adsorption on resin D301 (2012) Arabian J. Chem.Cocenza, D.S., Moraes, M.A., Beppu, M.M., Fraceto, L.F., Use of biopolymeric membranes for adsorption of paraquat herbicide from water (2012) Water Air Soil Pollut., 223, pp. 3093-3104Díaz, E.D.A., Velasco, M.C.V., Pérez, F.R., López, C.A.R., Ibarreta, L.L., UTILIZACÍON de adsorbentes basados em quitosana y alginato sódico para la eliminacíon de iones metélicos: Cu2+, Pb2+, Cr3+ y Co2+ (2007) Rev. Iberoam. Polímeros, 8, pp. 20-37Feng, C.Y., Khulbe, K.C., Matsuura, T., Ismail, A.F., Recent progresses in polymeric hollow fiber membrane preparation, characterization and applications (2013) Sep. Purification Technol., 111, pp. 43-71Giles, C.H., Macewan, T.H., Nakawa, S.H., Smith, D.J., Studies in adsorption. Part XI.* a system of classification of solution adsorption isotherms, and its use in diagnosis of adsorption mechanisms and in measurement of specific surface areas of Solids (1960) Chem. Soc., 3, pp. 3973-3993Ho, Y.S., Mckay, G., The kinetics of sorption of basic dyes from aqueous solution by sphagnum moss peat (1998) Can. J. Chem. Eng., 76, pp. 827-829Hu, Y.S., Zhao, Y.Q., Sorohan, B., Removal of glyphosate from aqueous environment by adsorption using water industrial residual (2011) Desalination, 271, pp. 150-156Linz, G.M., Homan, J., Use of glyphosate for managing invasive cattail (Typha spp.) to disperse blackbird (Icteridae) rostos (2011) Crop Prot., 30, pp. 98-104Ma, B., Qin, A., Li, X., Zhao, X., He, C., Bioinspired design and chitin whisker reinforced chitosan membrane (2014) Mater. Lett., 120, pp. 82-85Milojevic-Rakic, M., Janosevic, A., Krstic, J., Nedic Vasiljevic, B., Dondur, V., Ćiric-Marjonovic, G., Polyaniline and its composites with zeolite ZSM-5 for efficient removal of glyphosate from aqueous solution (2013) Microporous Mesoporous Mater., 180, pp. 141-155Monteiro Junior, O.A., Airoldi, C., The influence of chitosans with defined degrees of acetylation on the thermodynamic data for copper coordination (2005) J.Colloid Interface Sci., 282 (1), pp. 32-37Moon, G.Y., Pal, R., Huang, R.Y.M., Novel two-ply composite membranes of chitosan and sodium alginate for the pervaporation dehydration of isopropanol and ethanol (1999) J.Memb. Sci., 156, pp. 17-27Moraes, M.A., Cocenza, D.S., Vasconcellos, F., Fraceto, L.F., Beppu, M., Chitosan and alginate biopolymer membranes for remediation of contaminated water with herbicides (2013) J.Environ. Manag., 131, pp. 222-227Moreno Escobar, B., Gomez Nieto, M.A., Hontoria García, E., Simple tertiary treatment systems (2005) Water Supply, 5, pp. 35-41Motwani, S.K., Chopra, S., Talegaonkar, S., Kohli, K., Ahmad, F.J., Khar, R.K., Chitosan-sodium alginate nanoparticles as submicroscopic reservoirs for ocular delivery: formulation, optimization and invitro characterization (2008) Eur. J. Pharm. Biopharm., 68, pp. 513-525Ng, C., Losso, J.N., Marshall, W.E., Rao, R.M., Freundlich adsorption isotherms of agricultural by-product-based powdered activated carbons in a geosmin-water system (2002) Bioresour. Technol., 85, pp. 131-135Piccolo, A., Celano, G., Pietramellara, G., Adsorption of the herbicide glyphosate on a metal-humic acid complex (1992) Sci. Total Environ., pp. 77-82Qin, F., Wen, B., Shan, X.Q., Xie, Y.N., Liu, T., Zhang, S.Z., Khan, S.U., Mechanisms of competitive adsorption of Pb, Cu, and Cd on peat (2006) Environ. Pollut., 144, pp. 669-680(2009) The WHO Recommended Classification of Pesticides by Hazard, , http://www.who.int/ipcs/publications/pesticides_hazard_2009.pdf, International Programme on Chemical Safety, Stuttgart, Germany, Available at:, (accessed 02.06.14.)Yu, Y., Zhou, Q., He, Z., Effects of methamidophos and glyphosate on copper sorption-desorption behavior in soils (2005) Sci. China C Life Sci, 48, pp. 67-75Zhou, C., Wanga, Y., Li, C., Sun, R., Yu, Y., Zhou, D., Subacute toxicity of copper and glyphosate and their interaction to earthworm (Eisenia fetida) (2013) Environ. Pollut., 180, pp. 71-7

Genomics of quality traits

The quality attributes of cereal grains are valued in the context of a complex food chain that integrates outputs achievable by breeding, production, and processing. New processing technologies, environmental change, and changes in consumer preferences demand that quality attributes of wheat and barley need to be continually modified. The advances in the genomics of quality described in this chapter provide the basis for ensuring that the genetic approaches encompassing the complexities of the gene networks underpinning quality attributes can meet the challenges presented by the rapid changes occurring within the food chain