Chromatographic behaviour of phenols on thin layers of cation and anion exchangers. II. Dowex 50-X4 and Rexyn 102.

The chromatographic characteristics of 58 phenols on Rexyn 102 and Dowex 50-X4 thin layers in both the acidic and sodium salt forms have been studied, using elution with water, water-alcohol mixtures and aqueous salt solutions at different pH values. The influence of the percentage of alcohol, the pH and the ionic strength on the chromatographic behaviour of these phenols was investigated. The validity of the relationships among the RF values, the pH of the eluent and the pKa of the phenol has been verified on Dowex 50-X4 (Na+) thin layers. It has been shown that from the RFac, RFalk and pKa values of the different phenols, it is possible to predict their behaviour over the whole pH range and therefore to select the best conditions for their chromatographic separation.     

Force measurements on cell repellant and cell adhesive alginic acid coated surfaces

The atomic force microscope (AFM) was used to acquire force versus distance curves between the cantilever tip and samples bearing a surface overlayer of covalently linked alginic acid. The alginic acid coating resists cell-adhesion in in vitro experiments involving a normal and a tumor cell line. However, the surface becomes cell adhesive when alginic acid coated samples are subjected to glow discharge treatment. Force curves show in both cases the typical features resulting from the interaction between the cantilever tip and a hydrophilic, compressible polymer overlayer, suggesting that in both cases a diffuse interface with water exists. Following some recent findings on oligoethyleneglycol-terminated self-assembled-monolayers, it is suggested that conformational and molecular aspects of hydrophilic surface layers, rather than steric repulsion effects, could play a significant role in the mechanism that controls resistance to bio-adhesion.     

Physicochemical Properties of Solutions of Sodium Alginate Extracted from Brown Algae Laminaria Digitata

The rheological properties of sodium alginate solutions were studied as influenced by the concentration of alginic acid, pH of the medium, and temperature. The probable structural and conformational transformations induced on varying these parameters were suggested. The effect of cations and anions of varied nature on the viscous characteristics of these solutions was discussed.     

Pervaporation separation of water/alcohol mixtures using composite membranes based on polyelectrolyte multilayer assemblies

Composite pervaporation membranes composed of an asymmetric polyamide-6 membrane and an ultrathin self-assembled polyelectrolyte separating layer are described. The supporting membrane was prepared from both an unmodified polyamide-6 and a comb-like polymer with carboxyl terminated polyamide-6 side chains. A high end group concentration was found to be advantageous for sufficient adhesion of the multilayer systems on the supports. Up to 20 layers were deposited onto the membrane surface by dipping the membranes in aqueous solutions containing oppositely charged polyelectrolytes. The polyanions used were poly(acrylic acid), poly(styrene sulfonic acid) and alginic acid. The polycations used were poly(diallyldimethylammoniumchloride), chitosan and poly(ethylenimine). Performance of these membranes depends strongly on the layer number and on the type of polyelectrolytes. In general, membranes modified with two weak polyelectrolytes of high charge density gave the best separation properties while those modified with strong polyelectrolytes of low charge density led to poorer separation properties. However, the highest separation factor (≥10,000) for a water/2-propanol mixture (12/88 w/w) at permeate flux of 300 g/m²h was obtained with six double layers consisting of poly(ethylenimine) and alginic acid. These composite membranes were stable over an operating period of at least 400 h.     

Designing of pH-responsive ketorolac tromethamine loaded hydrogels of alginic acid: Characterization,in-vitro and in-vivo evaluation

pH-responsive hydrogels based on alginic acid grafted with acrylic acid and ethylene glycol dimethylacrylate in the presence of ammonium persulfate were developed for controlled delivery of Ketorolac tromethamine. The alginic acid based hydrogels were prepared by free radical polymerization technique. Increase in gel fraction was observed with the increase in alginic acid, acrylic acid, and ethylene glycol dimethylacrylate content. The dynamic swelling and drug release studies were conducted at two different pH values (pH 1.2 and 7.4). Maximum swelling and drug release were observed at pH 7.4. The characterization of prepared hydrogels was carried out by using Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, powder x-ray diffraction, and scanning electron microscopy. Similarly, in-vivo study was performed on rabbits and greater plasma drug concentration was achieved by fabricated hydrogels as compared to drug solution and commercial product Keten. Conclusively, the fabricated hydrogels can be considered as a potential candidate for controlled delivery of Ketorolac tromethamine.     

Polymer-Enhanced Ultrafiltration of Fe(III) and Cu(II) Aqueous Solutions Using Poly(Vinyl Alcohol)-Alginic Acid/Cellulose Membranes

This study deals with the removal of Fe(III) and Cu(II) from dilute aqueous solutions using a polymer-enhanced ultrafiltration process. The ultrafiltration studies were carried out in batch stirred cell and the applied pressure was controlled by nitrogen gas. Properties of the composite membranes and its application in metal removal from aqueous solutions were studied. A composite poly(vinyl alcohol)-alginic acid/cellulose membranes were prepared by coating poly(vinyl alcohol)-alginic acid mixture solutions on the filter paper. Poly(vinyl alcohol) and alginic acid were also used as complexing agents to enhance the retention of metal ions. In the filtration of Fe(III) and Cu(II) solutions, the effects of membrane contents, pressure and pH on the retention and the flux were studied. The maximum retention of metals was found as 99% for Fe(III) solution at pressure of 45 psi, pH of 3 in the presence of poly(vinyl alcohol) as complexing agent by using 0.50 (w/v)% [(75 Poly(vinyl alcohol)/25 Alginic acid) (w/w)]/cellulose composite membranes.     

Modeling investigation of membrane biofouling phenomena by considering the adsorption of protein, polysaccharide and humic acid

The importance of solute adsorption in the biofouling membrane has been clearly verified for the performance of membrane bioreactor (MBR). In order to quantify the mechanism of static adsorption in biofouling during of MBR process, we characterize membrane biofouling caused by model solutions containing a protein (bovine serum albumin, BSA), a humic substance (humic acid, HA) and a polysaccharide (alginic acid, Alg) on commercial hydrophilic polyethersulfone (PES) membrane. For static adsorption experiments, membranes were immersed in well-defined model solutions in three temperatures (298, 308 and 318 K) to obtain equilibrium data. To determine the characteristic parameters for this process, 7 isotherm models were applied to the experimental data. Three error analysis methods; the coefficient of nonlinear regression (R(2)), the sum of the squared errors (SSE) and standard deviation of residuals (S(yx)), were used to evaluate the data and determine the best fit isotherm for each model solutions. The error values demonstrated that the Sips isotherm model provided the best fit to the experimental data. AFM images were used for determination of changes in membrane surface after adsorption. These images confirmed the results obtained from adsorption isotherm study. Thermodynamic parameters such as standard free energy (Δ(r)G(θ)), enthalpy (Δ(r)H(θ)) and entropy (Δ(r)S(θ)) changes were determined; these adsorption processes were found to be feasible and endothermic but not spontaneous. The distribution of the substances adsorbed on PES surface were more chaotic than that in the aqueous solutions. Parameters obtained in this study can be used to determine the "fouling potential" of a given feed stream and a membrane.     

FT NIR Raman studies of alginic acid-benzimidazole polymer composite

New bio-inspired polymer composites of alginic acid and benzimidazole were created and characterized by FT NIR Raman spectroscopy. The obtained films with 1:0.5, 1:1 and 1:1.5 molar ratio are homogeneous, with good mechanical properties. Raman spectra recorded at room temperature revealed that the obtained films are a new compound with a different molecular structure and physical properties compared with pure substrates: alginic acid and benzimidazole. Raman band related to vibration of COOH entity at 1740 cm(-1) of alginic acid disappears in the alginic acid:benzimidazole composites, in which new Raman band related to COO(-) was found. Additionally, characteristic lines observed in polymer composites which may be associated with vibrations of NH groups, can be attributed to the linking of proton to deprotonated N atom in benzimidazole group. Possibility of such proton exchange is a promising property which might facilitate the application of obtained composites to anhydrous proton conducting electrolytes in fuel cells.     

Determination of arsenic,cadmium and zinc in river water by neutron activation analysis

A concentration apparatus has been developed for the determination of As, Cd and Zn in water by neutron activation. The preconcentration technique used for this purpose is based on the retention of As, Cd and Zn on the Rexyn 201 resin at pH 10. The apparatus used minimizes the manipulations needed for preconcentration and contamination by trace elements present in reagents. Eleven samples of water from rivers in the Montreal region were analyzed and the following concentrations were found (in μg/1): As 0.86–1.95, Cd 0.61–0.98 and Zn 4.6–12.9.     

Sequestration of organometallic compounds by natural organic matter. binding of trimethyltin(IV) by fulvic and alginic acids

The binding capacity of fulvic and alginic acids towards trimethyl tin(IV) cation was quantitatively determined in order to evaluate the sequestering ability of toxic organometallic compounds by natural organic matter. Investigations were performed in the pH range of natural waters (5–8.5) where the carboxylate groups, largely present in both sequestering agents, are the main binding sites. A chemical interaction model, according to which both the protonation of polyelectrolyte ligands and the hydrolysis of the organotin cation in NaCl aqueous solution were considered, was used to define the speciation of the systems under investigation. Measurements performed at different ionic strength values (0.1, 0.25, 0.5 and 0.7 mol L^?1, NaCl) allowed us to consider the dependence of stability constants on the ionic strength, and to calculate the formation constants at infinite dilution. Results obtained show the formation of the complex species TMT(L), TMT(L)₂ and TMT(L)(OH) for L = fulvic acid and TMT(L) for L = alginic acid, respectively. In order to compare the strength of interaction of these natural poly electrolytes with other analogous synthetic polyelectrolytes, measurements were also carried out on the trimethyltin(IV)–polyacrylate (5.1 kDa) system, and in this case the formation of TMT(L), TMT(L)₂ and TMT(L)(OH) species was found. Results show the following trend of stability for the species TMT(L) in the systems investigated: TMT–fulvate ≈ TMT–polyacrylate > TMT–alginate. On the basis of the stability data obtained, the lowest concentration of fulvic and alginic acids, able to act as sequestering agents towards triorganotin(IV) cation in the conditions of natural waters, was also calculated. Copyright © 2006 John Wiley & Sons, Ltd.     

Entrapment of invertase in an interpenetrated polymer network of alginic acid and poly (1-vinylimidazole)

In this work, we have investigated the synthesis and characterization of a proton conductor based on alginic acid and poly (1-vinylimidazole). The polymer network was obtained by mixing alginic acid and poly (1-vinylimidazole) at various stoichiometric ratios. The polymer electrolytes were characterized by elemental analysis and FT-IR spectroscopy. Invertase was entrapped in the polymer networks during complex formation. Additionally, the maximum reaction rate and Michaelis-Menten constant were investigated for the immobilized invertase. The temperature and pH optimization, operational stability and shelf life of the polymer network were examined.     

Reaction of Azidocarboxyethyl Alginic Acid with <Emphasis Type="Italic">N</Emphasis>-Nucleophiles

The acylating ability of azidocarboxyethyl alginic acid in reactions with benzylamine, aromatic amines, and carboxylic acid hydrazides has been studied.     

The formation of inclusion compounds of alginic acid in aqueous solution

From the microscopic visualization of metal alginates, the alginate fine structure was found to be a regularly arranged network having many host spaces in its fiber net. Under acid solution such a fiber net took the rounded, buckled and twisted form as much as possible and finally changed to a porous cluster form. Then the binding properties of sodium alginate, calcium or cadmium alginate and granular alginic acid obtained from the treatment with hydrochloric acid to iodine, cholesterol and dyes were investigated. Sodium alginate and calcium or cadmium alginate formed adducts with iodine, cholesterol and dyes; accordingly the amount of these materials in solution was reduced by the addition of alginates. The high uptake of alginates by these materials were cleary observed under acid solution giving inclusion compounds. Granular alginic acid also showed high uptake of iodine and dyes, but not of cholesterol. The blue stained alginate-iodine compound formed at pH about 1 having maximum absorption at 587nm was found to be an inclusion compound judging from the distance of 3.13 Å for included iodine I-I and the number of uronic residues bound to the iodine molecule in the granular alginic acid-iodine compound. The binding mechanism for the high uptake behavior of alginic acid was clarified with the observation of inclusion compounds by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).     

Retention of Large Biological Molecules by Size-Exclusion Chromatography

Size-exclusion chromatography has been developed for the separation of large biological molecules including proteins, polymers, peptides, nucleic acids, and polysaccharide according to their molecular size. This study determined the retention factors for dextran (5, 25, 50, 270, 670, and 1100?kDa) and polysaccharides, such as fucoidan, alginic acid, and laminarin, in the size-exclusion chromatography stationary phase. In addition, the molecular weights and retention factor of three polysaccharides were calculated from the dextran standard curve. The largest retention factor was 4.26 using the size-exclusion chromatography columns (5?kDa dextran). The molecular weights of fucoidan, alginic acid, and laminarin were determined to be 250, 200, and 5 to 64?kDa, respectively.     

Thermal analysis of ammonium,mono-, di- and triethanolammonium alginates

Thermal behaviour of ammonium (NH₄alg), mono- (MEAalg), di- (DEAalg) and triethanolammonium (TEAalg) salts of alginic acid (Halg) was investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Salts were prepared by the direct reaction of alginic acid with the ammonium hydroxide and with the respective ethanolamines. After preparation the compounds were lyophilized during 24 h and characterized by FTIR spectroscopy and elemental analysis (C, H and N). Under air the compounds exhibited three successive thermal decomposition steps: dehydration, decomposition of the polymeric matrix and finally, burning of carbonaceous residue. Under nitrogen two steps (dehydration and decomposition) were observed. The stability order of this series of compounds was: TEAalg this series of compounds was: TEAalg<DEAalg<NH₄alg<Halg≈MEAalg. DSC curves between –50 and 150°C did not show any thermal events suggesting that after lyophilization probably non-freezing type water is present in the system.     

Magnetic molecularly imprinted polymers for recognition and enrichment of polysaccharides from seaweed

New magnetic molecularly imprinted polymers with two templates were fabricated for the recognition of polysaccharides (fucoidan and alginic acid) from seaweed by magnetic solid‐phase extraction, and the materials were modified by seven types of deep eutectic solvents. It was found that the deep eutectic solvents magnetic molecularly imprinted polymers showed stronger recognition and higher recoveries for fucoidan and alginic acid than magnetic molecularly imprinted polymers, and the deep eutectic solvents‐4‐magnetic molecularly imprinted polymers had the best effects. The practical recovery of the two polysaccharides (fucoidan and alginic acid) purified with deep eutectic solvents‐4‐magnetic molecular imprinted polymers in seaweed under the optimal conditions were 89.87, and 92.0%, respectively, and the actual amounts extracted were 20.6 and 18.7 μg/g, respectively. To sum up, the developed method proved to be a novel and promising method for the recognition of complex polysaccharide samples from seaweed.     

Water-Soluble Polymers and Their Polymer-Metal Ion-Complexes as Antibacterial Agents

Summary: Natural and synthetic polymers with heteroatom, such as oxygen, nitrogen, sulfur or phosphorous, potentially can efficiently remove metal ions from aqueous solutions. The ability of synthetic polymers derived from imino diacetic acid, acrylamido glycolic copolymer, and the natural polymer alginic acid to remove metal ions from dilute solution in conjunction with ultrafiltration membranes was studied. The maximum retention capacity was determined and its polymer-metal ion-complexes were studied as possible antibacterial agents.     

Isolation of microbial DNA by newly designed magnetic particles

Carboxyl group-containing magnetic nonporous poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) (P(HEMA-co-GMA)) microspheres and cobalt ferrite nanoparticles modified with alginic acid (natural carboxylic polysaccharide) were used for isolation of microbial DNA of lactic acid bacteria (LAB) from dairy products, lyophilised cell cultures, and bacterial colonies grown on hard media, and Trichophyton fungi DNA from lyophilised cells. DNA from the samples with lysed cells was reversibly adsorbed to the particles in the presence of high poly(ethylene glycol) (PEG 6000) and sodium chloride concentrations. The optimal final PEG and NaCl concentrations were 9.1 wt.% and 2.0 M, respectively. The adsorbed DNA was released from the particles in low ionic strength TE buffer. The quality of isolated DNA was checked by PCR amplification. Moreover, PCR amplicons were isolated on cobalt ferrite nanoparticles modified with alginic acid and checked by restriction analysis.     

Trace determination of Ag(I) after reduction to Ag nanoparticles and sol–gel entrapment by alginic acid hydrogel

The main goal of this work is development of an effective analytical method for trace determination of Ag(I). The novelty of the Ag(I) preconcentration–determination method is mainly referred to the material and the enrichment–detection process (alginic acid gel phase was employed in a pH-switched sol–gel entrapment/Ag fluorescence detection). Ag(I) was reduced to Ag nanoparticles (AgNPs) and then was enriched by the alginic acid hydrogel phase. Then, the formed gel phase (containing AgNPs) was dissolved in alkali solution prior to Ag detection. The enrichment method was highly compatible with spectrofluorimetry, electrothermal atomic absorption spectrometry (ETAAS) and spectrophotometry. Optimization of the reduction-enrichment procedure was performed employing spectrofluorimetry. The linear working range (LWR) and limit of detection (LOD) for Ag(I) determination were found as 0.1–25 and 0.017 µmol L^??1, respectively. The effects of various anions, cations and organic chemicals on Ag(I) determination were spectrofluorimetrically studied. The applied enrichment-ETAAS Ag(I) determination method showed the LWR and LOD as 0.2–6.9 and 0.05 nmol L^??1, respectively. Also, an enrichment factor equal to 30.3 was obtained for the preconcentration method. The method was successfully applied to determine Ag in different water samples, jewels, antimicrobial suspensions and waste X-ray films. X-ray diffraction, transmission electron microscopy, field emission-scanning electron microscopy and EDX-mapping were also employed to characterize the entrapped AgNPs in the alginic acid gel phase. The complimentary experiments showed the alginic acid gel was also applicable for quantitative recovery of silver from the waste radiographic films.