Immobilization of glucoamylase on the plain and on the spacer arm‐attached poly(HEMA‐EGDMA) microspheres

Immobilization glucoamylase onto plain and a six‐carbon spacer arm (i.e., hexamethylene diamine, HMDA) attached poly(2‐hydroxyethylmethacrylate‐ethyleneglycol dimethacrylate) [poly(HEMA‐EGDMA] microspheres was studied. The microspheres were prepared by suspension polymerization and the spacer arm was attached covalently by the reaction of carbonyl groups of poly(HEMA‐EGDMA). Glucoamylase was then covalently immobilized either on the plain of microspheres via CNBr activation or on the spacer arm‐attached microspheres via CNBr activation and/or using carbodiimide (CDI) as a coupling agent. Incorporation of the spacer arm resulted an increase in the apparent activity of the immobilized enzyme with respect to enzyme immobilized on the plain of the microspheres. The activity yield of the immobilized glucoamylase on the spacer arm‐attached poly(HEMA‐EGDMA) microspheres was 63% for CDI coupling and 82% for CNBr coupling. This was 44% for the enzyme, which was immobilized on the plain of the unmodified poly(HEMA‐EGDMA) microspheres via CNBr coupling. The K_m values for the immobilized glucoamylase preparations (on the spacer arm‐attached microspheres) via CDI coupling 0.9% dextrin (w/v) and CNBr coupling 0.6% dextrin (w/v) were higher than that of the free enzyme 0.2% dextrin (w/v).The temperature profiles were broader for both immobilized preparations than that of the free enzyme. The operational inactivation rate constants (k_iop) of immobilized enzymes were found to be 1.42 × 10^?5 min^?1 for CNBr coupled and 3.23 × 10^?5 min^?1 for CDI coupled glucoamylase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2702–2710, 2001     

Graft copolymerization of 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method

An attempt has been made to graft copolymerize 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method in an aqueous medium. Polypropylene hydroperoxide has been prepared by irradiating recrystallized polypropylene beads from a Co⁶⁰ source in the presence of air. The resulting polypropylene hydroperoxide beads have been used as the backbone polymer and grafting of 4-vinyl pyridine has been studied as a function of various reaction parameters. Optimum conditions for maximum percentage of grafting have been evaluated. Rate of grafting (R_g) has been determined as a function of preirradiation dose and initial monomer concentration. Water has been found to affect percentage of grafting. The graft copolymers have been characterized by spectroscopic method and isolation of the grafted poly(4-VP) from the graft copolymer. A plausible mechanism is proposed to explain the mutual grafting of 4-vinyl pyridine onto polypropylene hydroperoxide. © 1993 John Wiley & Sons, Inc.     

Oxidation of aroylthioureas during their reactions with 2,3-diphenylcyclopropenone resulting in (E/Z)-3-(aroylthioureido)-2-phenylcinnamic acids

Isolated (E/Z)-3-(aroylthioureido)-2-phenylcinnamic acids have been obtained from the reactions of N-substituted-aroylthioureas with 2,3-diphenylcyclopropenone in acetic acid. The abnormal behavior of the reaction was described as due to nucleophilic addition of N ³ followed by hydrolysis, ring opening and oxidation processes.     

Glucose oxidase immobilization onto a plasma-induced graft copolymerized polymeric membrane modified by poly(ethylene oxide) as a spacer

Plasma-induced graft copolymerization of acrylic acid, which was incorporated onto polyethylene (PE) film, was prepared. A bisamino poly(ethylene oxide) (PEO) was immobilized onto the poly(acrylic acid) (PAAc)-grafted PE membrane to modify the surface properties. The samples were characterized by ESCA. A respective chemical shift of Ar plasma-treated and control polymeric film was revealed by ESCA. The presence of the grafted PAAc and PEO was also verified. Glucose oxidase (GOD) was immobilized onto this novel grafted polymeric film with and without PEO being used as a spacer. The Michaelis constant, K_m, and the maximum reaction velocity, V_max, were estimated for the free and the immobilized GOD. GOD immobilized onto the polymeric films with and without a spacer obeyed Michaelis kinetics. The Michaelis constant, K_m, was larger for the immobilized GOD than for the free one whereas V_max was smaller for the immobilized GOD. The bioactivity of PEO-modified PAAc-grafted PE membrane (PAAc–PEO–GOD) was higher than that of PAAc-grafted PE membrane (PAAc–GOD). The pH and thermal stabilities of the immobilized GOD without a spacer (PAAc–GOD) were higher than those of the immobilized GOD with a spacer (PAAc–PEO–GOD) and the free form. © 1993 John Wiley & Sons, Inc.     

The synthesis of bi- and trichromophoric dyes bearing an s-triazinyl ring spacer

An alternative procedure has been described for the syntheses of several bi- and trichromophoric compounds consisting of 1-aminopyrene and 3-aminobenzanthrone chromophoric subsystems connected by an s-triazinyl ring spacer. The synthetic method used, which utilises an autoclave under autogenous pressure, is suitable for the nucleophilic substitution of both chlorine atoms within the triazinyl ring by weakly basic aromatic amines. The structures of the synthesized compounds were confirmed using elemental analysis, ¹H NMR, and mass spectra. UV/vis absorption and fluorescence spectra and fluorescence quantum yields were measured. The dependence of fluorescence intensity and fluorescence quantum yields on solvent polarity was investigated.     

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

Poly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL^?1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adsorption of IgG on spacer‐arm and L‐arginine ligand attached poly(GMA/MMA/EGDMA) beads

This work presents data on human immunoglobulin G (HIgG) adsorption onto L ‐arginine ligand attached poly(GMA/MMA/EGDMA)‐based affinity beads which were synthesized from methyl methacrylate (MMA) and glycidiyl methacrylate (GMA) in the presence of a crosslinker (i.e., ethylene glycol dimethacrylate; EGDMA) by suspension polymerization. The epoxy groups of the poly(GMA/MMA/EGDMA) beads were converted into amino groups after reaction with ammonia or 1,6‐diaminohexane (i.e., spacer‐arm). With L ‐arginine as a ligand, it was covalently immobilized on the aminated (poly(GMA/MMA/EGDMA)‐ AA) and/or the spacer‐arm attached (poly(GMA/MMA/EGDMA)‐SA) beads, using glutaric dialdehyde as a coupling agent. Both affinity poly(GMA/MMA/EGDMA)‐based beads were used in HIgG adsorption/desorption studies under defined pH, ionic strength, or temperature conditions in a batch reactor, using acid‐treated poly(GMA/MMA/EGDMA) beads as a control system. The poly(GMA/MMA/EGDMA)‐SA affinity beads resulted in an increase in the adsorption capacity to HIgG compared with the aminated counterpart (i.e., poly(GMA/MMA/EGDMA)‐AA). The maximum adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA affinity beads were found to be 112.36 and 142 mg g^?1, and the affinity constants (K_d), evaluated by the Langmuir model, were 2.48 × 10^?7 and 6.98 × 10^?7M, respectively. Adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA were decreased with HIgG by increasing the ionic strength adjusted with NaCl. Adsorption kinetic of HIgG onto both affinity adsorbents was analyzed with first‐ and second‐order kinetic equations. The first‐order equation fitted well with the experimental data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 672–679, 2007     

New approach for evaluating the risk of hydrate formation during transport of hydrocarbon hydrate formers of sI and sII

Classical industrial hydrate risk evaluation schemes are commonly based on water dew-point calculation. This method ignores another (new) route to hydrate formation based on adsorption of water onto rusty surfaces. Maximum allowable water contents in pure and mixtures of hydrate formers of Structures I and II hydrocarbons to avoid the risk of hydrate nucleation during pipeline transport have been studied using both the dew-point method and the new approach of adsorption of water onto hematite (rust). The estimates from this study suggest that the new approach (adsorption of water onto the rusty internal walls of pipelines and equipment) dominates. Thus, this approach could have an impact on designing natural gas dehydration systems. Free energy analysis has also been performed to show which molecule forms hydrate first based on the combined first and second laws of thermodynamics in terms of Gibbs free energy. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1097–1110, 2019     

Influence of Spacer Nature on the Aggregation Properties of Anionic Gemini Surfactants in Aqueous Solutions

A series of anionic gemini surfactants with the same structure except the spacer nature have been studied. Their solution properties were characterized by the equilibrium surface tension and intrinsic fluorescence quenching method. The critical micelle concentrations (CMC), surface tension at cmc, C₂₀, and the micelle aggregation number (N) were obtained. The surface tension measurements indicate that these gemini surfactants have much lower cmc values and great efficiency in lowering the surface tension of water compared with those of conventional monomeric surfactants. Furthermore, the standard free energy of micellization for anionic gemini surfactants was also determined. The results showed that the nature of the spacer has an important effect on the aggregation properties of gemini surfactants in aqueous solutions. The surfactant with a hydrophilic, flexible spacer was more readily able to form micelle compared with the surfactant with a hydrophobic, rigid spacer, which leads to a lower CMC value, larger N, more negative free energy of micellization, and a more closely packed micelle structure.     

Sorption kinetics for the removal of dyes from effluents onto chitosan

The ability of chitosan, a biosorbent obtained by the processing of waste seafood shells, to remove five acid dyes from effluents has been studied. Chitosan is a deacetylated bio‐polymer of chitin. The effect of varying initial dye concentration on the rate of adsorption has been investigated. The rate data have been analyzed using three kinetic models, namely, a pseudosecond order, the Ritchie modified second order, and the Elovich models. The sorption kinetics of Acid Green 25, Acid Orange 10, Acid Orange 12, Acid Red 18, and Acid Red 73 onto chitosan can be best correlated by the Elovich equation. The kinetic model was determined in accordance with the agreement between the rate equations and the differentiation of kinetic equations. The values of rate constants for the three models are in the range of 0.003–2.230, 0.004–0.237, and 0.0173–405 for the pseudosecond order, the Ritchie modified second order and the Elovich models, respectively. The sensitivity analysis, by plotting the reciprocal of the rate, Z_L = (d_q/d_t)^?1 against time, is used to identify the true kinetic model. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Catalytic activity of polymer–montmorillonite composites in chemical reactions

Polymer–clay composite material has been prepared by intercalation of polymeric ammonium salt onto the montmorillonite (Na–MMT) followed by grafted polymerization of hydroxyethyl methacrylate onto amine‐terminated poly(butadiene‐co‐acrylonitrile)–montmorillonite (ATBN–MMT) intercalate. The hydroxyl groups were modified to chloromethyl groups followed by conversion to onium salts, which are suitable as phase transfer catalysis. The catalytic activities of the supported catalysts were investigated in nucleophilic reactions of thiocyanate and cyanate ions with alkyl and aryl halides. The rates of the reactions have been investigated under different factors such as the nature and structure of the support, the amount of catalyst, the solvent, and the temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1121–1129, 2006     

Sulfonic Derivatives of 2-Mercaptobenzoxazole and Its Conjugates with Poly(Maleic anhydride-alt-vinyl acetate) with Potential Pharmacological Applications

The results reported represent a continuation of the research on the synthesis of new 2-mercaptobenzoxazole derivatives with potential pharmacological activity and corresponding conjugates prepared by chemical immobilization through ester and amidic bonds onto poly(maleic anhydride-alt-vinyl acetate). New sulfonic compounds derived from 2-mercaptobenzoxazole were synthesized in order to obtain substances with a nucleophilic capacity. Their immobilization on copolymer support, based on poly(maleic anhydride-alt-vinyl acetate) through ester or amidic bonds led to polymer—biologically active principle conjugates with controlled release capacity. Release of the compound immobilized by ester bonds was found to take place in the first 5–6 h. The 2-mercaptobenzoxazole derivatives and the conjugates were characterized using elemental and spectral analysis (FT-IR, ¹H-NMR). Toxicological and antimicrobial tests were performed, recommending some of these therapeutics as candidates for pharmacological applications.     

Introduction of quaternary amines onto a film surface by graft polymerization

Quaternary amines were introduced onto a poly(ethylene terephthalate) (PET) film surface by two different methods using UV-induced graft polymerization. The first involves a two-step reaction: graft polymerization of N,N′-(dimethylamino)ethyl methacrylate (DMAEMA) onto the PET film, followed by quaternization of the tertiary N,N′-dimethylamino groups of grafted chains using alkyl bromides (R_nBr). The second is direct graft polymerization of DMAEMA having pendant quaternary amines onto the PET film. The alkyl bromides used for quaternization of the monomers and graft chains include: n-propyl, n-butyl, n-octyl, n-lauryl, and n-cetyl bromide. The two-step method could quaternarize 90% of the pendant N,N′-dimethylamino groups of the graft chains when R₃Br was used. The extent of quaternization decreased with the increasing carbon number of alkyl bromide. The direct one-step method gave a graft amine density of 8 nmol/cm² when the monomer quaternized with R₃Br was used for the graft polymerization in the presence of 1 X 10^-3M sodium metaperiodate. The carbon number of alkyl chains in the quaternary amines estimated from XPS spectra was in good agreement with that of R_nBr used for quaternization. © 1996 John Wiley & Sons, Inc.     

Protection of 4-Fluoroanisole from Aromatic Nucleophilic Photosubstitution by Cyclodextrins [1]

Aromatic nucleophilic photosubstitution reactions of 4-fluoroanisole with cyanide and water have been investigated in aqueous α-β-, and γ-cyclodextrin solutions. Although photoreactivity of the α- or β-cyclodextrin-complexed 4-fluoroanisole toward nucleophilic substitution is suppressed almost completely, none of the cyclodextrins had a measurable influence on the rate of 4-fluoroanisole fluorescence quenching by I⁻. In aqueous γ-cyclodextrin, the efficiency of photohydroxylation was increased slightly but the efficiency of photocyanation was unaffected. From Benesi-Hildebrand plots, the dissociation constants of the complexes of 4-fluoroanisole with α- and β-cyclodextrins were obtained. A good correlation between the relative quantum yields and the degree of complexation was found. Explanation for the lack of a marked effect on photosubstitution by γ-cyclodextrin is presented.     

Associating behaviour of polyacrylamide modified with a new hydrophobic zwitterionic monomer

The nucleophilic ring opening of dicyanoketene ethylene acetal by tertiary amino monomers leads to an hydrophobic zwitterionic monomer [(dimethylammonioethoxy)dicyanoethenolate]propylmethacrylamide (DADPMA) characterized by a very high dipole moment. Hydrophobically modified water soluble polymers have been prepared by classical radical polymerization of acrylamide and DADPMA either in homogeneous medium (water/ethanol mixtures) or in micellar solution (water containing sodium dodecylsulphate (SDS)). The copolymers obtained have a high molecular weight (M _w = 2–5 × 10⁶ g mol^?1) and are water soluble for a content of DADPMA lower than 1% mole/mole. The properties of the copolymers in aqueous solution depend on the synthesis conditions, especially on the ratio ethanol:zwitterionic monomer. © 2001 Society of Chemical Industry     

Effect of diffusional resistances on the action pattern of immobilized alpha-amylase

Alpha-amylase from Aspergillus oryzae has been immobilized onto corn grits and porous silica (specific areas 180 and 440 m² g^?1). Kinetic parameters of immobilized enzyme have been determined. Immobilization of alpha-amylase results in the formation of less polymerized products resulting in an apparent decrease in the number of transglycosylation reactions, for both maltotetraose and starch as substrates, when compared with free enzyme. Diffusional limitations for substrate and products have been quantified in the case of the three supports used. External diffusional resistances were important in all cases for the reaction products, whilst they became negligible for the substrate in the case of silica supports. Moreover, internal transfer limitations were identified with silica 180 m²g^?1 support. It was demonstrated that diffusional resistances were in direct relation to the apparent modification of the enzyme action pattern after immobilization.     

Novel batch reactor design for the adsorption of arsenate on chitosan

BACKGROUND: The sorption of arsenate, a poison of acute toxicity found in natural waters, onto chitosan, a biosorbent derived from waste seafood shells has been studied. A batch adsorber design model was developed to determine how much chitosan adsorbent is required to reduce the arsenate concentration in solutions to the WHO standard of 10 µg L^?1. RESULTS: A series of batch kinetic experiments has been carried out at different initial pH values. The initial arsenate sorption appears to be completed after 30 min, however, a steady reversible reaction takes place resulting in the desorption of arsenate over 48 h. These phenomena in the batch kinetic data have been correlated simultaneously using the newly developed pseudo‐first order reversible model. Two batch reactor design models have been developed and compared. The first model is a conventional approach based on the equilibrium isotherm capacity equation. A second batch adsorption reactor design is based on the principle of contacting time required, t_max, for the chitosan to achieve its maximum adsorption capacity, q_max. The practical outcome from the second batch adsorber model results in a saving in adsorbent mass per batch of approximately 39.4%, 96.2% and 92.3% chitosan adsorbent at pH conditions of 3.5, 4.0 and 5.0, respectively. CONCLUSION: The adsorbent cost and handling costs are reduced in the second batch adsorber model. There is also a significant savings in the batch turnaround time required in the batch adsorber design when the design is based on the maximum adsorption capacity rather than the equilibrium adsorption capacity. Copyright © 2010 Society of Chemical Industry     

Synthesis and properties of novel random and block copolymers composed of phthalimidine‐ and perfluoroisopropylidene‐polyarylether‐sulfones

A series of novel polyarylethersulfone (AB) _n block copolymers with different segment lengths have been synthesized by nucleophilic solution polycondensation of phenoxide‐terminated and fluorine‐terminated oligomers; random copolymers have been prepared over the whole composition ranges. The structures of the resultant copolymers have been confirmed by FTIR, ¹³C NMR spectra and differential scanning calorimetry (DSC). Compared with two homopolymers and random copolymers, the block copolymers of this study possess excellent thermal stability (5% thermal decomposition under nitrogen atmosphere above 500 °C) and high glass transition temperatures, and have a wide melt‐processing temperature range. They may become a new class of mouldable high performance thermoplastics. © 2001 Society of Chemical Industry     

Synthesis and characterization of N‐vinyl pyrrolidone and cellulosics based functional graft copolymers for use as metal ions and iodine sorbents

To develop cost effective and eco friendly polymeric materials for enrichment and separation technologies, 1‐vinyl‐2‐pyrrolidone (N‐VP) was graft copolymerized onto cellulose, extracted from pine needles. Optimum conditions have been evaluated for the grafting of N‐VP onto cellulose and at these conditions it was also grafted onto cellulose phosphate, hydroxypropyl cellulose, cyanoethyl cellulose, and deoxyhydrazino cellulose. At the optimum grafting conditions for N‐VP, it was also cografted with maleic anhydride. Kinetics of radiochemical graft copolymerization has been studied and evaluation of the polymerization and grafting parameters as percent grafting, percent grafting efficiency, rate of polymerization, homopolymerization, and graft copolymerization have been evaluated. Graft copolymers have been characterized by elemental analysis, FTIR, and swelling studies. An attempt has been made to study sorption of some metal ions such as Fe²⁺ and Cu²⁺ and iodine on select graft copolymers to investigate selectivity in metal ion sorption and iodine sorption as a function of structural aspects of the functionalized graft copolymers to find their end uses in separation and enrichment technologies. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 373–382, 2005     

Influence of Nature of Spacer and Hydrocarbon Chain Length on Micellar Encapsulation of Polynuclear Aromatic Hydrocarbons by Carbohydrate Derived Non-Ionic Gemini Surfactants in Aqueous Ethanol Medium

Gemini surfactants with rigid aromatic spacer -CH₂-Ar-CH₂-: 6,6′-(N,N′-di(alkyl)-1,4-phenylenedimethylamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) and Gemini surfactants with flexible aliphatic spacer -(CH₂)₆-: 6,6′-(N,N′-di(2-hydroxyalkyl)-1,6-hexanediamino)bis(6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose) have been synthesized, and their micellar properties for encapsulation of polynuclear aromatic hydrocarbons (PAH) viz. fluorene, anthracene, triptycene, and pyrene in aqueous ethanol medium have been studied by means of electronic spectroscopy. The micellar study reveals that nature of spacer and length of hydrocarbon chain of the surfactant has profound effect on micellar encapsulation of PAH. The surfactants with rigid aromatic spacer show greater encapsulation as compared to surfactants with flexible aliphatic spacer. Moreover, the more hydrophobic surfactant, i.e. the surfactant with a longer hydrocarbon chain, shows greater encapsulation toward PAH which are encapsulated in the order of their smaller size.