Microwave assisted synthesis of polyacrylamide grafted agar (Ag-g-PAM) and its application as flocculant for wastewater treatment

Grafting of polyacrylamide (PAM) chains was performed onto the backbone of Agar by microwave assisted method, using microwave radiation in synergism with ceric ammonium nitrate (CAN) as the chemical free radical initiator. The intended grafting of the PAM chains were confirmed through intrinsic viscosity study, FTIR spectroscopy and elemental analysis (C, H, N, O & S). Further characterization of the grafted product was done in form of SEM morphology and TGA study. Flocculation efficacy of the synthesized graft copolymers was studied in kaolin suspension, through ‘Jar test’ procedure. Further, flocculation efficacy of the ‘best grade’ (as determined by ‘jar test’ in kaolin suspension) in wastewater was studied for possible application in reduction of pollutant load of wastewater.     

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.     

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.     

Microwave initiated synthesis of polyacrylamide grafted Psyllium and its application as a flocculant

This paper reports a novel microwave initiated method for synthesis of polyacrylamide grafted Psyllium (Psy-g-PAM). Psyllium was modified through grafting of polyacrylamide (PAM) chains on it using microwave radiations only, in absence of any other free radical initiator. The grafting was confirmed by intrinsic viscosity study and characterization techniques like FTIR spectroscopy, elemental analysis (C, H, N, O and S) and SEM morphology study. Further, the flocculation efficacy of the synthesized graft copolymers was studied in kaolin and coal fine suspension through standard 'Jar test' procedure.     

Study of polyacrylamide grafted starch based algal flocculation towards applications in algal biomass harvesting

Microalgae may be the source of high amount of lipid and protein. It has the property for carbon dioxide sequestration, recycling and also can remove pollutants from wastewater. Using traditional methods, collection of algal biomass is either cost effective, time consuming or may be toxic due to use of chemical salts. The aim of this study is to harvest freshwater microalgae (Chlorella sp. CB4) biomass by using polymer. Polyacrylamide grafted starch (St-g-PAM) has been synthesized by microwave assisted method involving a synergism of microwave radiation and ceric ammonium nitrate (CAN) to initiate the grafting reaction. The synthesis was optimized in terms of CAN and monomer (acrylamide) concentration. The algal flocculation efficacy of all the grades of this graft copolymer was studied through standard 'Jar test' procedure. Effects of percentage grafting, pH and zeta potential on percentage recovery of algal biomass were thoroughly investigated.     

Microwave assisted synthesis of polyacrylamide grafted starch (St-g-PAM) and its applicability as flocculant for water treatment

Polyacrylamide grafted starch (St-g-PAM) was made by a novel method of synthesis, involving combination of microwave radiation and a chemical free radical initiator (ceric ammonium nitrate) to initiate grafting reaction. This method (microwave assisted synthesis) is quick, highly reliable, reproducible and yields high quality product as compared to the conventional method (which uses a chemical free radical initiator alone to initiate the grafting reaction).The St-g-PAM grades synthesized were characterized by various physicochemical techniques. Further, its application as flocculant for wastewater treatment was investigated.     

Characterization and evaluation of methyl methacrylate-acetylated Saccharum spontaneum L. graft copolymers prepared under microwave

Hybridization of the natural polymers with synthetic polymers is of great interest because of its application to biomedical and biodegradable materials. Synthesis of graft copolymers of methyl methacrylate (MMA) onto acetylated Saccharum spontaneum L. fiber using ferrous ammonium sulphate–potassium per sulphate (FAS–KPS) redox initiator under the influence of microwave radiation (MWR) was carried-out. Different reaction parameters such as time, initiator molar ratio, monomer concentration, microwave power, pH and solvent were optimized to get maximum graft yield (72.2%). On grafting, percentage crystallinity decreases rapidly with reduction in its stiffness and hardness. The graft copolymers thus formed were characterized by FTIR, SEM, XRD, TGA, DTA and DTG techniques. Moreover, graft copolymers have been found to be more moisture resistant and also showed higher chemical and thermal resistance.     

Characterisation of carboxymethyl cellulose and polyacrylamide graft copolymer

The synthesis of carboxymethyl cellulose-g-polyacrylamide was carried out by a ceric ion induced solution polymerization technique. By varying the amount of catalyst and monomer, six different grades of graft copolymers were synthesized. These graft copolymers were characterized by elemental analysis, infrared spectroscopy, rheological studies, scanning electron microscopy, thermal analysis, viscosity measurement and X-ray diffractometry. They exhibit distinguished flocculation characteristics in various suspensions and effluents. Their flocculation and viscosifying characteristics are drastically enhanced on their hydrolysis.     

Creating a unique environment for selecting reactive enzymes with DNA: 'Sticky' binding of oligocation-grafted polymers to DNA

To provide colloidally stable polyplexes formed between pDNA and cationic polymers, cationic polymers have been modified with hydrophilic polymers to form a hydrophilic shell. Block copolymers of cationic and hydrophilic polymers and cationic polymers grafted with hydrophilic polymers are representative designs of such polymers. Here, we report a new design of cationic polymers and oligocationic peptide-grafted polymers. We synthesized 15 kinds of graft copolymers by varying the number of cationic charges of the peptides and their grafting density. We found that graft copolymers with less cationic peptides and less grafting density formed colloidally stable polyplexes. Interestingly, the less cationic graft copolymers bind to excess amounts of pDNA. We also found that the graft copolymers showed selectivity toward reactive enzymes affording the reaction of pDNA with nucleases, while suppressing both the replication of DNA by DNA polymerase and gene expression. The suppression of the replication and expression is considered to result from the high capacity of the graft copolymers for binding with pDNA. The polynucleotides produced by DNA polymerase or RNA polymerase would be captured by the graft copolymers to impede these enzymatic reactions.     

Cationic tamarind kernel polysaccharide (Cat TKP): A novel polymeric flocculant for the treatment of textile industry wastewater

Synthesis of cationic tamarind kernel polysaccharide (Cat TKP), its detailed physicochemical characterization and application as an efficient flocculant for the treatment of textile industry wastewater have been investigated. N-3-Chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC) was used as a cationic reagent to introduce quaternary amine groups onto the backbone of tamarind kernel polysaccharide (TKP). Various grades were synthesized to obtain the optimized one. Effect of reaction parameters onto the degree of cationization has also been investigated. The synthesized polymers were characterized by various macromolecular characterization techniques, which confirm that cationization does take place. Afterwards, the applicability of TKP and various grades of Cat TKP's as flocculants for the treatment of textile industry wastewater was investigated. The flocculation experiments showed that TKP alone contributes little to the flocculation. However, cationic TKP led to significant improvement as flocculant for the treatment of textile industry wastewater. The best performing Cat TKP (i.e. Cat TKP 3) was thereafter compared with a commercial flocculant, which is cationic in nature. It has been observed that Cat TKP 3 surpasses the flocculation efficiency over commercial flocculant.     

A new method of controlled grafting modification of chitosan via nitroxide-mediated polymerization using chitosan-TEMPO macroinitiator

The controlled graft modification of chitosan has first been achieved by nitroxide-mediated polymerization using chitosan-TEMPO macroinitiator. Chitosan-TEMPO macroinitiator was obtained from the (60)Co gamma-ray irradiation of N-phthaloylchitosan and 4-hydroxy-TEMPO in DMF under argon atmosphere. The graft copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR), Fourier transform infrared spectrometer (FT-IR), X-ray powder diffractometer (XRD) and high performance particle sizer (HPPS). The results indicate that the graft copolymers were successfully synthesized and that the graft polymerization was well controlled by the nitroxide-mediated process. The size distribution of chitosan-g-polystyrene in benzene is very narrow, which may be associated with the "well-defined" polystyrene (PSt) onto chitosan from nitroxide-mediated polymerization. This work provides a new method to prepare chitosan grafting copolymers with controlled molecular weights and "well-defined" structures.     

Redox recognition using “click” chemistry

The ferrocenyl-triazolyl dendrimers synthesized by Huisgen-type Cu^I-catalyzed 1,3-dipolar cycloaddition of ferrocenyl acetylenes with azido-terminated dendritic cores serve as redox exo-receptors for the recognition of both transition-metal cations and oxo-anions. This mini-review focuses on this work originated from the authors’ laboratory.     

Microwave initiated synthesis of polymethylmethacrylate grafted guar (GG-g-PMMA), characterizations and applications

Guar gum was grafted with polymethylmethacrylate (PMMA) by microwave initiated method. The synthesis was optimized for highest percentage grafting, by varying the microwave irradiation time and monomer (methyl methacrylate) concentration. The various grades of grafted product (GG-g-PMMA) were characterized through standard physicochemical characterization techniques (intrinsic viscosity measurement, elemental analysis, FTIR spectroscopy & SEM morphology study). Further, flocculation efficacy of this grafted polysaccharide was studied by standard 'Jar test' procedure in 0.5% kaolin suspension, to assess its application as flocculating agent for wastewater treatment and mineral ore beneficiation. Correlation between percentage grafting and intrinsic viscosity was also studied for the possibility of using it as a tool to control the intrinsic viscosity in the final product. This leads to the possibility of application of the grafted product as superior viscosifier than guar gum.     

Recent advances in polysaccharide bio-based flocculants

Natural polysaccharides, derived from biomass feedstocks, marine resources, and microorganisms, have been attracting considerable attention as benign and environmentally friendly substitutes for synthetic polymeric products. Besides many other applications, these biopolymers are rapidly emerging as viable alternatives to harmful synthetic flocculating agents for the removal of contaminants from water and wastewater. In recent years, a great deal of effort has been devoted to improve the production and performance of polysaccharide bio-based flocculants. In this review, current trends in preparation and chemical modification of polysaccharide bio-based flocculants and their flocculation performance are discussed. Aspects including mechanisms of flocculation, biosynthesis, classification, purification and characterization, chemical modification, the effect of physicochemical factors on flocculating activity, and recent applications of polysaccharide bio-based flocculants are summarized and presented.     

Flocculation: an alternative process to ion-exchange chromatography: (A scale-up study using recombinant human superoxide dismutase as model protein).

Flocculation using pellicular charged flocculants was investigated as an alternative process to conventional chromatography in purification of recombinant proteins using human recombinant superoxide dismutase expressed in E. coli as a model system. The removal of pyrogens, proteins, debris and the yield were determined. At laboratory scale, the starting conditions were optimized to yield a stable solution and the flocculation process fitted into a purification scheme. 100 L fermentation broth was the initial volume at pilot scale. The process parameters determined at the laboratory scale were tested and the results were compared to the pilot scale. The method was also compared to an ion-exchange chromatography.     

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.     

Immobilization of Saccharomyces cerevisiae on to modified carboxymethylcellulose for production of ethanol

In this work, modified carboxymethylcellulose (CMC) was used as a new support material for production of ethanol. Crosslinked graft copolymers of CMC with N-vinyl-2-pyrrolidone (N-VP) were prepared in different grafting yields. The beads material was characterized by means of fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), scanning electron microscope (SEM) and swelling experiment. Saccharomyces cerevisiae was immobilized using entrapment method in the graft copolymers of carboxymethylcellulose-g-poly(N-vinyl-2-pyrrolidone) (CMC-g-PVP) for ethanol fermentation. The effects of grafting yield, initial glucose concentration and crosslinker concentration on the yield of ethanol process were investigated. Reusability of the immobilized yeasts was investigated and found that the materials can be used four times without losing their activity. Ethanol production increased to 59.3 g/L from 46.4 g/L when percentage of N-VP in the graft copolymer was increased. The highest ethanol productivity was found to be 1.75–2.25 g/L h. Fermentation time decreased with the decreasing of crosslinker concentration. The results suggest that the proposed method for immobilization of Saccharomyces cerevisiae has potential in industrial applications for ethanol process.     

Xanthan-g-poly(acrylamide): Microwave-assisted synthesis,characterization and in vitro release behavior

Xanthan-g-poly(acrylamide) was synthesized employing microwave-assisted and ceric-induced graft copolymerization, and was characterized by FT-IR, DSC, XRD and SEM studies. Matrix tablets of diclofenac sodium were formulated using graft copolymer as the matrix by direct compression technique. Release behavior of the graft copolymer was evaluated using USP type-II dissolution apparatus in 900 ml of phosphate buffer (pH 6.8), maintained at 37 °C and at 50 rpm. Microwave-assisted grafting provided graft copolymer with higher % grafting in a shorter time in comparison to the ceric-induced grafting. The % grafting was found to increase with the increase in the power of microwave and/or time of exposure. The matrix tablets were found to release the drug by zero-order kinetics, and the faster release of drug was observed from the graft copolymer matrix as compared to the xanthan gum matrix. It was observed that grafting reduces the swelling, but increases the erosion of xanthan gum.     

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.     

Graft copolymerization of methyl methacrylate onto mercaptochitin and some properties of the resulting hybrid materials

The graft copolymerization of methyl methacrylate onto mercaptochitin and some properties of the resulting graft copolymers have been studied. Methyl methacrylate was efficiently graft copolymerized onto mercaptochitin in dimethyl sulfoxide, and the grafting percentage reached 1300% under appropriate conditions. Although the side-chain ester groups were resistant to aqueous alkali, hydrolysis could be achieved with a mixture of aqueous sodium hydroxide and dimethyl sulfoxide. Subsequent treatment with acetic anhydride in methanol transformed the sodium carboxylate groups into carboxyl groups. Although the graft copolymers exhibited an improved affinity for organic solvents, those having sodium carboxylate or carboxyl units were characterized by a much more enhanced solubility and were soluble in common solvents. The hygroscopic nature of chitin decreased with an increase in the grafting extent but increased significantly upon hydrolysis of the ester groups. The enzymatic degradability of the graft copolymers, as evaluated with lysozyme, was also dependent on the grafting extent and much higher than that of the original chitin. DSC measurements revealed the presence of a glass transition phenomenon, which could be ascribed to the poly(methyl methacrylate) side chain.