Temperature-responsive cellulose by ceric(IV) ion-initiated graft copolymerization of N-isopropylacrylamide

Temperature-responsive cellulose has been obtained by graft copolymerization of N-isopropylacrylamide (NIPAAm) monomer using ceric ammonium nitrate (CAN) as initiator at 25.0 +/- 0.1 degrees C in acidic medium. Kinetic and grafting parameters were evaluated at different concentrations of NIPAAm ranging from 1.25 x 10(-3) to 12.5 x 10(-3) mol dm(-3) and varying concentrations of CAN from 1.5 x 10(-3) to 9.0 x 10(-3) mol dm(-3) at constant concentration of nitric acid (2.5 x 10(-2) mol dm(-3)). The graft copolymerization of NIPAAm onto cellulose has shown a significant increasing trend below lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAAm) and shown low energy of activation (18.0 kJ mol(-1)) for graft copolymerization within the temperature range of 10-35 degrees C as determined with Arrhenius plot. The PNIPAAm-grafted cellulose has shown improved thermal stability and shown temperature-dependent degree of swelling. Variation in degree of swelling of PNIPAAm-grafted cellulose as a function of temperature has been used to determine LCST of PNIPAAm-grafted cellulose. The contact angle (theta) has shown variation on increasing the graft yield and temperature. On the basis of experimental observations, the reaction steps for graft copolymerization have been proposed and a rate expression has been derived.     

Synthesis and properties of a water soluble graft (chitosan-g-2-acrylamidoglycolic acid) copolymer

The present paper reports the graft copolymerization of 2-acrylamidoglycolic acid onto chitosan by using potassium bromate/silver nitrate as an efficient redox initiator in an inert atmosphere. The effect of reaction conditions on grafting parameters i.e. grafting ratio, efficiency, conversion, add on, homopolymer and rate of grafting has been studied. Experimental results show that maximum grafting has been obtained at 0.4 g dm(-3) concentration of chitosan, 8.0×10(-2) mol dm(-3) concentration of 2-acrylamidoglycolic acid and 1.0×10(-3) mol dm(-3) concentration of hydrogen ion. It has also been observed that grafting ratio, add on, conversion, efficiency and rate of grafting increase up to 3.2×10(-3) mol dm(-3) of silver nitrate and 1.7×10(-2) mol dm(-3) of potassium bromate. Time (120 min) and temperature (40°C) were kept constant during reaction. The physicochemical properties of graft copolymer synthesized have been performed in terms of water swelling, metal ion sorption, flocculation and resistance to biodegradability with respect to the chitosan as a parent polymer. The graft copolymer has been characterized by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis.     

Syntheses and characterisation of graft copolymers of maize starch and methacrylonitrile

Grafting of methacrylonitrile (MAN) onto dried maize starch using ceric ammonium nitrate (CAN) as an initiator has been studied gravimetrically under nitrogen atmosphere in aqueous medium. The percentage grafting is favoured by increasing monomer concentration and reaction time but is affected by higher concentration of initiator and high temperature. No grafting was observed beyond 45°C. The optimum conditions established for grafting were: [CAN]=0.002 mol/l which was added in molar nitric acid; [MAN]=0.755 mol/l; reaction time, 180 min; and temperature, 35°C. The graft copolymers were analyzed by infrared spectroscopy and acid hydrolysis. The grafting of methacrylonitrile onto starch does not alter the thermal stability of starch. The crystalline region of starch was also involved in grafting. Scanning electron microscopy showed a thick polymer coating of grafted PMAN on the starch surface.     

Synthesis, characterization and applications of graft copolymer (κ-carrageenan-g-vinylsulfonic acid)

The synthesis of graft copolymer (κ-carrageenan-g-vinylsulfonic acid) is carried out in nitrogen atmosphere using potassium peroxymonosulfate (PMS) and malonic acid (MA) as redox system. The effect of reaction variables including the concentration of vinylsulfonic acid 1.3×10(-2) to 6.7×10(-2) mol dm(-3), PMS 4×10(-3) to 20×10(-3) mol dm(-3), MA 1.6×10(-3) to 4.8×10(-3) mol dm(-3), sulfuric acid 1×10(-3) to 8×10(-3) mol dm(-3), κ-carrageenan 0.4-1.8 g dm(-3) as well as time duration 60-180 min and temperature 25-45 °C has been studied. The water swelling capacity of graft copolymer is investigated. Flocculation property for both coking and non-coking coals is studied for the treatment of coal mine waste water. The graft copolymer has been characterized by FTIR and thermogravimetric analysis.     

Graft copolymerization of methyl acrylate onto pullulan using ceric ammonium nitrate as initiator

Water absorption resins of pullulan graft methyl acrylate (PU-g-MA) using ceric ammonium nitrate (CAN) as an initiator has been investigated under nitrogen atmosphere in aqueous medium. The percentage grafting (%PG) is favoured by increasing reaction time but is affected by higher concentration of initiator and monomer, and high temperature. Experiments showed that the optimal conditions for grafting were: [CAN] = 0.004 mol/l which was added in 1 mol/l nitric acid; [MA] = 0.0465 mol/l; reaction time; 180 min and temperature, 40 °C. The graft copolymer was analyzed by infrared spectroscopy. The water absorption capacity of the resins decreased significantly with the increase in %PG.     

Formation and morphology of struvite and newberyite in aqueous solutions at 25 and 37 degrees C

The influence of the initial reactant concentrations (c(i)(Mg)tot = 5.0 x 10(6) to 5.0 x 10(-1) mol dm(-3), c(i)(P)tot = c(i)(NH4)tot = 1.0 x 10(-3) to 5.0 x 10(-1) mol dm(-3)) and temperature (25 and 37 degrees C) on the composition and morphology of the precipitates formed in the system MgCl2-NH4H2PO4-NaOH-H2O at initial pHi = 7.40 has been investigated. Precipitation diagrams are presented showing the concentration regions within which different morphologies of solid phase have been formed. The solid phases aged for 24 hours were characterized by means of optical microscopy, FT-IR spectrophotometry, X-ray diffractometry and thermogravimetry. It was found that struvite was a predominant phase formed within the concentration region examined and newberyite was obtained only in the region where pH(24h) < 6.5. The influence of the initial pH on the formation and transformation of these two compounds were studied in the region 5.0 < or = pHi < or = 9.0 and the results are discussed.     

Synthesis, characterization and thermal sensitivity of chitosan-based graft copolymers

Novel chitosan-based graft copolymers (CECTS-g-PDMA) were synthesized through homogeneous graft copolymerization of (N,N-dimethylamino)ethyl methacrylate (DMA) onto N-carboxyethylchitosan (CECTS) in aqueous solution by using ammonium persulfate (APS) as the initiator. The effect of polymerization variables, including initiator concentration, monomer concentration, reaction time and temperature, on grafting percentage was studied. XRD, FTIR, DSC and TGA were used to characterize the graft copolymers. Surface-tension measurements, turbidity measurements and temperature-variable (1)H NMR analysis were combined to investigate the thermal sensitivity of CECTS-g-PDMAs in aqueous solution.     

Polyacrylamide grafted Agar: Synthesis and applications of conventional and microwave assisted technique

Polyacrylamide grafted Agar (Ag-g-PAM) has been successfully synthesized by conventional method and microwave assisted method. The former method employs ceric ammonium nitrate (CAN) as the free radical initiator while the latter uses the combination of ceric ammonium nitrate (CAN) and microwave irradiation. The synthesized graft copolymers have been characterized by elemental analysis (C, H, N, O and S), FTIR spectroscopy, intrinsic viscosity measurement and scanning electron micrograph (SEM); taking agar as a reference. Flocculation efficacy of synthesized graft copolymers was studied in kaolin suspension and in waste water through 'Jar test' procedure. In the present investigation, we have observed that polyacrylamide grafted agar synthesized by microwave assisted technique shows superior properties than conventional technique. These properties are reported in terms of intrinsic viscosity, flocculation efficacy and pollutant load reduction of waste water.     

Study of graft copolymerization of N-maleamic acid-chitosan and butyl acrylate by gamma-ray irradiation

N-maleamic acid-chitosan was synthesized and characterized by Fourier transform infrared spectra analysis (FT-IR) and 1H NMR. The graft copolymerization of N-maleamic acid-chitosan and butyl acrylate (BA) in acetic acid aqueous solution was investigated, using the gamma-ray of 60Co gamma-irradiation method. DSC (differential scanning calorimetry) trace of N-maleamic acid-chitosan-g-PBA has a glass-transition temperature (Tg) at -42 degrees C. The thermal stabilities of the graft copolymer were studied by the thermal gravimetric analysis (TGA). The effect of synthesis variables in the graft copolymerization have been discussed in the light of grafting efficiency, grafting percentage, and homopolymer percentage. Increasing grafting percentage was observed when the monomer concentration and total dose were increased or when the reaction temperature was decreased.     

HRP-based biosensor for monitoring rifampicin

Pyrrole was electropolymerized onto a Pt electrode in the presence of LiClO(4) and horseradish peroxidase (HRP). This HRP-based biosensor has been used for the amperometric detection of rifampicin (RIF) in the presence of a constant concentration of H(2)O(2). The C(H(2)O(2)) as well as the applied potential (E(ap)) and the pH of the phosphate buffer have simultaneously been optimized through a central composite design. Under these conditions, repeatability, reproducibility, and stability of the modified electrode have been analyzed. The detection limit for RIF has been calculated taking into account the probability of false-positive (alpha) and -negative (beta), reaching a value of 5.06x10(-6) mol dm(-3). The biosensor was applied to the determination of RIF in pharmaceutical preparations and biological samples.     

Synthesis and characterization of a new polysaccharide-graft-polymethacrylate copolymer for three-dimensional hybrid hydrogels

Hybrid materials constituted by hydrophobic and hydrophilic biocompatible macromolecules are useful for biomedical applications. In this context, a well-known acrylic monomer (methyl methacrylate) was polymerized and grafted onto the polysaccharide dextran by the use of ceric ammonium nitrate as a redox initiator in aqueous nitric acid medium. The effects of concentrations of dextran, acrylic monomer, and ceric ions on the copolymerization yields were investigated in detail. The obtained polymers were studied by solubility measurements, Fourier transform infrared spectrometry, (13)C nuclear magnetic resonance spectroscopy, and viscosimetric analysis. Interestingly, we found conditions to form transparent and homogeneous thin films or 3D structures with hybrid properties. Indeed, the copolymer, but not dextran or PMMA, could be dissolved in water/THF (20/80 v/v). The thermomechanical properties of the resulting copolymer analyzed by differential scanning calorimetry and dynamic mechanical analysis showed the occurrence of a single glass-transition temperature and a marked difference with the two homopolymers. The cytocompatibility of the copolymer with human endothelial cells was evidenced by the normal cell adhesion, proliferation, and morphology after 5 days in culture on these gels. In conclusion, this type of copolymer with hybrid properties of two biocompatible macromolecules could be of great interest as a 3D scaffold or for coating in biomedical applications.     

Chain scission of hyaluronan by peroxynitrite

The reaction of peroxynitrite with the biopolymer hyaluronan has been studied using stopped-flow techniques combined with detection of molecular weight changes using the combination of gel permeation chromatography and multiangle laser light scattering. From the effect of peroxynitrite on the yield of hyaluronan chain breaks, it was concluded that the chain breaks were caused by hydroxyl radicals which escape a cage containing the *OH NO*(2) radical pair. The yield of free hydroxyl radicals was determined as 5+/-1% (as a proportion of the total peroxynitrite concentration). At high peroxynitrite concentrations, it was observed that the yield of chain breaks leveled out, an effect largely attributable to the scavenging of hydroxyl radicals by nitrite ions present in the peroxynitrite preparation. These experiments also provided some support for a previous proposal that the adduct formed between ONOOH and ONOO(-) might itself produce hydroxyl radicals. The rate of this reaction would have to be of the order of 0.05 s(-1) to produce hydroxyl radical yields that would account quantitatively for chain break yields at high peroxynitrite concentrations. By carrying out experiments at higher hyaluronan concentrations, it was also concluded that an additional yield of chain breaks was produced by the bimolecular reaction of the polymer with ONOOH at a rate constant of about 10 dm(3)mol(-1)s(-1). At 5.3 x 10(-3)mol dm(-3) hyaluronan, this amounted to 3.5% chain breaks (per peroxynitrite concentration). These conclusions support the proposal that the yield of hydroxyl radicals arising from the isomerization of ONOOH to nitrate ions is relatively low.     

Bacterial sensors based on Acidithiobacillus ferrooxidans Part I. Fe2+ and S2O32- determination

An amperometric bacterial sensor with current response to Fe(2+) and S(2)O(3)(2-) ions has been designed by immobilizing an acidophilic biomass of Acidithiobacillus ferrooxidans on a multi disk flat-front oxygen probe. The bacterial layer was located between the oxygen probe and a membrane of cellulose. A filtration technique was used to yield the bacterial membranes having reproducible activity. The decrease of O(2) flow across the bacterial layer is proportional to the concentration of the dosed species. The dynamic range appeared to be linear for the Fe(2+) ions up to 2.5 mmol L(-1) with a detection limit of 9 x 10(-7) mol L(-1) and a sensitivity of 0.25 A L mol(-1). The response of the biosensor is 84 s for a determination of 2 x 10(-4) mol L(-1) Fe(2+). Optimizing the Fe(2+) determination by A. ferrooxidans sensor was carried out owing to Design of Experiments (DOE) methodology and empirical modelling. The optimal response was thus obtained for a pH of 3.4, at 35 degrees C under 290 rpm solution stirring. S(2)O(3)(2-) concentration was determined at pH 4.7, so avoiding its decomposition. The concentration range was linear up to 0.6 mmol L(-1). Sensitivity was 0.20 A L mol(-1) with a response time of 207 s for a 2 x 10(-4) mol L(-1) S(2)O(3)(2-) concentration.     

GMA grafted sago starch as a reactive component in ultra violet radiation curable coatings

Glycidyl methacrylate (GMA) was successfully grafted onto sago starch using ceric ammonium nitrate as initiator in aqueous medium. The percentage of grafting increased with increasing concentration of GMA monomer in the range studied. A core-shell configuration had been suggested to account for the hydrophobic behavior of the starch-g-GMA. Fourier transform infrared spectral analysis provided evidence of the grafting of GMA onto the starch. The acrylic double bond participated in the grafting onto the polysaccharide backbone with the glycidyl groups remaining unaffected.

The graft copolymer of starch and glycidyl methacrylate (starch-g-GMA) was incorporated into UV curable formulations using a cationic photoinitiator. In general, the addition of starch-g-GMA increased the flexibility of the cured film. The increasing of starch-g-GMA concentration in the coatings formulation increased the hardness of cured films. Gel content of the cured epoxy resin remained unimpaired by the addition of starch-g-GMA. Increasing the photoinitiator concentration in the coating formulations increased the hardness and as expected decreased the flexibility of the cured film. The gel content increased with increasing photoinitiator concentration. Further experiments are in progress to study the biodegradability of coatings.     

Modification of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) film by chemical graft copolymerization

The graft copolymerization of 2-hydroxyethylmethacrylate (HEMA) onto poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) films has been investigated. The graft copolymerization was conducted in aqueous media using benzoyl peroxide (BPO) as chemical initiator. PHBHV films were prepared by solvent casting. Different parameters affecting the graft yield were studied such as monomer concentration, initiator concentration, and reaction time. The extent of grafting has been modulated by the preparation conditions, in particular the concentration of HEMA. However, it is interesting to note that the initiator concentration had only a slight influence on the graft yield. Characterization of the grafted PHBHV films assumed that the graft copolymerization not only occurred on the film surface but also took place into the film bulk. Differential scanning calorimetry showed that crystallinity dramatically decreased with increasing graft yield, indicating that graft copolymerization hindered the crystallization process. Wettability has been obviously improved by grafting a hydrophilic monomer such as HEMA for high graft yield (>130%).     

Synthesis,structure and properties of new tung oil-styrene-divinylbenzene copolymers prepared by thermal polymerization

A variety of new polymers ranging from rubbery materials to tough and rigid plastics have been prepared by the thermal copolymerization of tung oil, styrene, and divinylbenzene. The thermal copolymerization is performed in the temperature range of 85-160 degrees C with variations in the stoichiometry, oxygen uptake, peroxides, and metallic catalysts used. Gelation of the reactants typically occurs at temperatures higher than 140 degrees C, and fully cured thermosets are obtained after post-curing at 160 degrees C. The fully cured thermosets are determined by Soxhlet extraction to contain approximately 90-100% cross-linked materials, and (1)H NMR and FTIR spectroscopy indicates that the cross-linked materials are random copolymers. The new bulk polymeric materials obtained are light yellow and transparent with glossy surfaces, and possess glass transition temperatures of -2 to +116 degrees C, cross-link densities of 1.0 x 10(3)-2.5 x 10(4) mol/m(3), coefficients of linear thermal expansion of 2.3 x 10(-4)-4.4 x 10(-4) per degrees C, compressive moduli of 0.02-1.12 GPa, and compressive strengths of 8-144 MPa. These materials are thermally stable below 300 degrees C and exhibit a major thermal degradation with a maximum degradation rate at 493-506 degrees C.     

The rate constants of the reaction of hydroxyl radicals (*OH) with alcohol dehydrogenase and Glyceraldehyde-3-phosphate dehydrogenase

The rate constants of the reactions of alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase with hydroxyl radicals were determined using the method of steady-state competitive reactions. Ethanol was used as a scavenger of hydroxyl radicals. The rate constants of the reactions of hydroxyl radicals with alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase were found to be 2.8 x 10(12) dm(3) mol(-1) s(-1), and 1.6 x 10(12) dm(3) mol(-1) s(-1), respectively.     

A novel polymeric flocculant based on polyacrylamide grafted carboxymethylstarch

Novel functionalized polymeric flocculants based on polyacrylamide grafted carboxymethylstarch (CMS-g-PAM) have been successfully synthesized via conventional method (using ceric ammonium nitrate as free radical initiator, in an inert atmosphere) as well as by using microwave irradiation (‘microwave initiated’ synthesis). Under optimal grafting conditions, 50% grafting has been observed in case of the microwave irradiation based method and 47% grafting has been observed in case of the conventional process. The synthesized graft copolymers have been characterized by elemental analysis, FTIR spectroscopy, intrinsic viscosity measurement, molecular weight determination, ¹³C NMR spectroscopy and scanning electron micrograph (SEM); taking carboxymethylstarch (CMS) as reference. The effects of reaction parameters onto the percentage of grafting have been studied. Further, the applicability of these grafted polymers as flocculants for the treatment of municipal sewage wastewater has also been investigated.     

A novel nitric oxide biosensor based on electropolymerization poly(toluidine blue) film electrode and its application to nitric oxide released in liver homogenate

A novel poly(toluidine blue)-modified electrode has been constructed for the determination of nitric oxide in biological sample. The electrochemical behavior of poly(toluidine blue) film electrode and its electrocatalytic activity toward NO were studied in detail by cyclic voltammetry. Possible interferences were tested and evaluated after further coated with Nafion. The poly(toluidine blue) and Nafion composite film-modified electrode exhibits a good linear relationship over a NO concentration of 1.8 x 10(-7) to 8.6 x 10(-5)mol/L, and the detection limit is 1.8 x 10(-8)mol/L (S/N=3). NO release from the rat liver homogenate stimulated by l-arginine was studied, and the responses were decreased by the nitric oxide synthase inhibitor N(omega)-nitro-l-arginine.     

Pulse radiolysis studies of beta-carotene in oxygenated DMSO solution. Formation of beta-carotene radical cation

The spectroscopic and kinetic characteristics of beta-carotene radical cation (beta-carotene(.+)) were studied by pulse radiolysis in aerated DMSO solution. The buildup of beta-carotene(.+) with k(1) = (4.8 +/- 0.2) x 10(8) dm(3) mol(-1) s(-1) [lambda(max) = 942 nm, epsilon = (1.6 +/- 0.1) x 10(4) dm(3) mol(-1) cm(-1)] results from an electron transfer from beta-carotene to DMSO(.+). The beta-carotene(.+) species decays exclusively by first-order reaction, k = (2.1 +/- 0.1) x 10(3) s(-1), probably by two processes: (1) at low substrate concentration by hydrolysis and (2) at high concentrations also by formation of dimer radical cation (beta-carotene)(2)(.+). Under the experimental conditions, a small additional beta-carotene triplet-state absorption ((3)beta-carotene) in the range of 525 to 660 nm was observed. This triplet absorption is quenched by oxygen (k = 7 x 10(4) s(-1)), resulting in singlet oxygen ((1)O(2)), whose reactions can also lead to additional formation of beta-carotene(.+).