Kinetic investigations on the alkaline hydrolysis of tris-(1,10-phenenthroline)Fe(II) with guar gum–surfactant interactions

The kinetic investigations on the alkaline hydrolysis of tris-(1,10–phenanthroline)iron(II) has been explored spectrophotometrically in microheterogeneous environment at 301?K and ionic strength of 0.13?mol?L^?1. Guar gum, cationic amphiphiles, and their mixtures are used as the reaction environments to carry out the reaction. Guar gum decreases the rate of reaction, which indicates that Fe(II) complex may be trapped in the hydrophobic region of gum. Cationic amphiphile decreases the rate in the presence of guar gum. The extent of interaction between guar gum and amphiphile increases with the hydrophobic carbon chain length. The critical aggregation concentration (CAC) and critical micelle concentration (CMC) of the amphiphiles (cetyl trimenthyl ammonium bromide (CTAB), tetradecyl trimenthyl ammonium bromide (TTAB), dodecyl trimenthyl ammonium bromide (DTAB)) in the presence of guar gum have been determined with conductometry and tensiometry. All observations support either weak or strong interaction of cationic amphiphiles with guar gum. Activation parameters of the reaction in different environments have been determined which corroborate the rate data.     

Synthesis of cationic guar gum-graft-polyacrylamide at low temperature and its flocculating properties

Acrylamide grafted cationic guar gum (CGG-g-PAM), induced by ceric ammonium sulfate, was synthesized using aqueous polymerization technique at 10 °C and the flocculation property was studied with high-turbidity tobacco wastewater (NTU > 4500). Thus five grades of graft copolymers were obtained through alteration of initiator and monomer concentrations in order to understand the effect of molecular weight on flocculation. The grafted copolymer was characterized by FTIR and SEM. Study of DTG demonstrated that CGG-g-PAM had better heat-resistant performance than guar gum, cationic guar gum (CGG) and polyacrylamide. The dosage of polyaluminium chloride (PAC) and CGG-g-PAM, pH value and molecular weight were considered to be the factors that can influence flocculation efficiency. The result showed best flocculation efficiency occurs at pH 5 when the dosage of CGG-g-PAM and PAC are 3.6 ppm and 120 ppm, respectively. The percentage of turbidity and COD removal are 98% and 24% correspondingly, and its flocculating efficiency prevails over that of CGG and cationic polyacrylamide (CPAM).     

Gas chromatographic determination of polysaccharide gums in foods after hydrolysis and derivatization

A gas chromatographic method was evaluated for the determination of food grade gums in dairy products, salad dressings and meat sauces. The gums studied were tragacanth, karaya, ghatti, carob, guar, arabic and xanthan gum. The extraction method included removal of fat followed by starch degradation then precipitation of protein. The isolated gums were hydrolysed with trifluoroacetic acid and the resulting neutral monosaccharides converted to their aldonitrile acetate derivatives for determination by gas chromatography. Recoveries from thirteen different commodities averaged 85%. However, the recovery of guar gum from ice cream and cold pack cheese was 42 and 50%, respectively. In a comparison of enzyme hydrolysis and iodine complexation for the removal of starch the former was simpler and provided cleaner extracts than the iodine treatment. Both gave similar results.     

Some chemical and analytical aspects of polysaccharide modifications. II. A high-yielding,specific method for the chemical derivatization of galactose-containing polysaccharides: Oxidation with galactose oxidase followed by reductive amination

A versatile and high-yielding method was developed for specifically modifying galactose-containing polysaccharides, exemplified here by two representative galactomannans, guar gum 1 and locust bean gum 5 . Oxidation of the primary alcohol functions of 1 and 5 with galactose oxidase produced the corresponding aldehyde derivatives 2 and 6 which were subsequently derivatized in several ways. Reductive amination with sodium cyanoborohydride of 2 and 6 proceeded smoothly (60–90% yields) and led to stable amine derivatives ( 4 , 7–11 ), which included hydroxyalkylamine- ( 8 ), glycine- ( 9 ), and BSA- ( 11 ) derivatives. The cationic primary amine derivative 12 was similarly reductively alkylated with lactose to yield a product 13 with extended carbohydrate side chains. Oxidation of 2 produced the anionic carboxy derivative 14 , whereas reduction of 2 and 6 with sodium borodeuteride yielded the deuterium labeled neutral species 15 and 16 . The undegraded gums and some of their derivatives were studied by high resolution ¹³C-NMR (100.6 MHz) at 30°C, and the proposed chemical shift assignments were in good qualitative agreement with those of earlier studies. ESR spectroscopy was used to follow the chemical reactions and to derive information about the galactose distribution of 1 and 5 . Mean nearest neighbor distances (r?) between nitroxides attached to 1 and 5 were 1.36 nm (±5%) for 4 and 1.75 nm (±5%) for 7 . These r? values agree favorably with the structural models recently proposed elsewhere, excluding earlier suggestions of homogeneous galactose distributions or regularly alternating blocks of branched and unbranched mannose units. The solution properties, such as viscosity and salt- and organic solvent-compatibility, of some of the guar derivatives appear to be unique and interesting. An alternative oxidation procedure of the galactose residues of 1 and 5 with sodium periodate has been evaluated.     

Investigational Studies on Highly Purified Fenugreek Gum as Emulsifying Agent

In this study, highly purified galactomannan containing fenugreek gum was isolated by newly reported method and investigated for its surface and emulsification property. Comparative studies were carried out with other galactomannan containing natural emulsifiers like locust bean gum, guar gum, and non-galactomannan anionic xanthan gum. The results revealed that highly purified fenugreek gum has better surface and interfacial tension reducing property among all gums used in this study. Emulsion prepared with 0.6% highly purified fenugreek gum showed greater reduction in droplets size with greater surface area compared to guar gum, locust bean gum, and xanthan gum emulsion. Zeta potential values indicated that highly purified fenugreek gum emulsion showed greater repulsive forces and was able to form more stable emulsion compared to other gums. No coalescence or phase separation was observed during storage.      

Interaction of gums (guar, carboxymethylhydroxypropyl guar, diutan, and xanthan) with surfactants (DTAB, CTAB, and TX-100) in aqueous medium

The interaction of surfactants dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB), and p-tert-octylphenoxypolyoxyethylene (9.5) ether (TX-100) with guar (Gr), carboxymethylhydroxypropyl guar (CMHPG), diutan (Dn), and xanthan (Xn) gums has been studied employing conductometry, tensiometry, microcalorimetry, viscometry, and atomic force microscopy (AFM) techniques. Both weak and strong interactions were observed. CTAB interacted stronger than DTAB with the gums. The surfactant-gum interaction process was enhanced by the presence of borate ions in the solution; the borate ion itself also manifested interaction with the surfactants comparable with that of water-soluble polymers polyvinyl alcohol, polyoxyethylene, and so forth. Viscometric results supported configurational changes of the gum molecules by interaction with surfactants. The geometry of the pure gums and their CTAB interacted products in the dried states was ascertained from AFM measurements; spherical and prolate shapes were observed for pure gums, and distorted states were observed for their surfactant complexed species. Detailed topological features of these entities were ascertained.     

Polyacrylamide Grafted Carboxymethyl Tamarind (CMT-g-PAM): Development and Application of a Novel Polymeric Flocculant

Water is scarce commodity now. Recycling of municipal wastewater, industrial and mineral processing effluents require treatment with the inorganic or organic flocculants. Both synthetic and natural polymers are used as flocculants. Natural polymers are biodegradable and are effective at very large dosages but are very shear stable. The synthetic polymers are highly effective flocculants at very small dosages and have high tailorability, but have poor shear stability. In the authors' laboratory, a novel polymeric flocculant has been developed by grafting polyacrylamide onto the backbone of carboxymethyl tamarind (CMT-g-PAM). Various grades were developed to optimize the best flocculant. The grafted polymers were characterized by various characterization techniques such as intrinsic viscosity measurement, FTIR spectroscopy, ¹³C-NMR spectroscopy, elemental analysis etc. The flocculation studies were carried out using turbidity test as well as settling test. The optimized CMT-g-PAM was then compared with some of the commercial flocculants available in national and international markets in colloidal suspensions and it has been found that our synthesized flocculant surpasses most of the commercial flocculants in performance.     

Comparative study of thermal degradation behavior of graft copolymers of polysaccharides and vinyl monomers

The thermal degradation of graft copolymers of both polysaccharides (guar gum and xanthan gum) showed gradual decrease in mass loss. Pure guar gum degraded about 95% but pure xanthan gum degraded about 76% up to 1173.15 K, while graft copolymers of guar gum and xanthan gum degraded only 65–76% up to 1173.15 K. Acrylic acid grafted guar gum and xanthan gum showing two-step degradation with formation of anhydride and ketonic linkage during heating, same pattern of degradation was found for xanthan gum-g-methacrylic acid. Guar gum-g-acrylamide degraded in single step and xanthan gum-g-acrylamide started to degrade above 448.15 K and it is a two-stage process and imparts thermal stability due to the formation of imide linkage with evolution NH₃. Guar gum-g-methacrylamide degraded in three steps due to the loss of NH₃ and CO₂ successively. 4-vinyl pyridine grafted both polysaccharides show single step degradation due to loss of pyridine pendent. N-vinyl formamide grafted guar gum and xanthan gum started to degrade at about 427.15 K, showed two-stage degradation process with the evolution of CO and NH₃ molecules while guar gum-g-(N-vinyl-2-pyrrolidone) degraded into two steps by the loss of pyrrolidone nucleus. Gum-g-2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) showed two-step degradation processes in two successive degradation steps, while xanthan gum-g-AMPS has started degradation at about 427.15 K and completed in five degradation steps. Overall, it was found that the grafted polysaccharides are thermally more stable than pure polysaccharides.     

Preparation and flocculating properties of highly substituted cationic starches of different vegetable origins

Kinetic regularities of flocculation of model kaolin suspensions by highly substituted cationic flocculants synthesized from different starches (corn, waxy corn, potato, and tapioca starches) have been studied as depending on the doses and vegetable origins of the flocculants. The rate of kaolin suspension flocculation has been found to increase with the dose of the cationic starches of all types. It has been shown that, irrespective of the dose, the highest rate of kaolin sedimentation in the model systems is observed in the presence of cationic potato starch. It has been demonstrated that cationic potato starch flocculates kaolin suspensions with concentrations of 0.1, 0.5, and 1.0% with the same efficiency. In this case, the suspensions are almost completely clarified within 2–5 min. Moreover, the dependence of the flocculating efficiency for a 0.1% model suspension on the dose of cationic starch has been found to pass through a maximum at a starch content of 1.0–5.0 mg/g of kaolin depending on the type of starch.     

Synthesis and Characterization of a Modified Chitosan

Chitosan has been modified by incorporating a cationic moiety N- (3-chloro 2-hydroxypropyl) trimethyl ammonium chloride (CHPTAC) onto its primary amine group in aqueous alkali medium. A series of modified chitosan copolymers (Chito-cat-1 to Chito-cat-5) was synthesized by varying the CHPTAC to chitosan ratio. The modified chitosan copolymers have been characterized by viscometry, elemental analysis, infrared spectroscopy (IR), thermal analysis and X-ray diffractometry. From the above investigations, it has been confirmed that the cationic moiety was successfully incorporated onto chitosan.     

Gas chromatographic-mass spectrometric characterisation of plant gums in samples from painted works of art

This paper presents an analytical GC-MS procedure to study the chemical composition of plant gums, determining aldoses and uronic acids in one step. The procedure is based on the silylation of aldoses and uronic acids, released from plant gums by microwave assisted hydrolysis, and previously converted into the corresponding diethyl-dithioacetals and diethyl-dithioacetal lactones. Using this method only one peak for each compound is obtained, thus providing simple and highly reproducible chromatograms. The analytical procedure was optimised using reference samples of raw plant gums (arabic, karaya, ghatti, guar, locust bean and tragacanth, cherry, plum and peach gums), commercial watercolours and paint layers prepared according to ancient recipes at the Opificio delle Pietre Dure of Florence (Italy). To identify gum media in samples of unknown composition, a decisional schema for the gum identification and the principal component analysis of the relative sugar percentage contents were employed. The procedure was used to study samples collected from wall paintings from Macedonian tombs (4th-3rd centuries bc) and from the Mycenaean "Palace of Nestor" (13th century bc) in Pylos, Greece. The presence of carbohydrates was ascertained and plant gum binders (fruit and a mixture of tragacanth and fruit tree gums) were identified in some of the samples.     

Rheological behavior and particle suspension capability of guar gum: sodium tetraborate decahydrate gels containing cellulose nanofibrils

Guar gum (GG) fracturing fluids were studied by incorporating cellulose nanofibrils (CNFs) in anhydrous borax crosslinked guar gum gels. To fully understand the impact of CNF on the proppant suspension capability of developed fracturing fluids, their shear rate-dependent viscosity and viscoelasticity were investigated. The shear rate dependencies of fluids was fitted to the Carreau model. The zero shear rate viscosity and elasticity of fracturing fluids increased significantly by incorporating CNF in guar gum gels. On the other hand, the viscosity at high shear rates (>100 s^?1) decreased as desired. The proppant settling velocities through fracturing fluids were evaluated by modeling the terminal falling velocity of proppants moving through a Carreau model fluid. The experimental results of the rheological behavior and the modeling results of the proppant settling rate indicated that the fracturing fluids containing CNF had better suspension capabilities. In addition, the lower viscosities of CNF formulated GG gels at higher shear rates will make them more pumpable.     

Determination of locust bean gum and guar gum by polymerase chain reaction and restriction fragment length polymorphism analysis

A polymerase chain reaction (PCR) was developed to differentiate the thickening agents locust bean gum (LBG) and the cheaper guar gum in finished food products. Universal primers for amplification of the intergenic spacer region between trnL 3' (UAA) exon and trnF (GAA) gene in the chloroplast (cp) genome and subsequent restriction analysis were applied to differentiate guar gum and LBG. The presence of <5% (w/w) guar gum powder added to LBG powder was detectable. Based on data obtained from sequencing this intergenic spacer region, a second PCR method for the specific detection of guar gum DNA was also developed. This assay detected guar gum powder in LBG in amounts as low as 1% (w/w). Both methods successfully detected guar gum and/or LBG in ice cream stabilizers and in foodstuffs, such as dairy products, ice cream, dry seasoning mixes, a finished roasting sauce, and a fruit jelly product, but not in products with highly degraded DNA, such as tomato ketchup and sterilized chocolate cream. Both methods detected guar gum and LBG in ice cream and fresh cheese at levels <0.1%.     

Identification of Leguminosae gums and evaluation of carob-guar mixtures by capillary zone electrophoresis of protein extracts

A procedure for the extraction and capillary zone electrophoresis (CZE) separation of proteins from carob, guar and tara gums in a background electrolyte (BGE) of pH 9 containing 0.1% polyvinyl alcohol is described. The CZE protein profiles exhibit characteristic peaks for each one of the Leguminosae gums, which can be used to construct models capable of identifying samples of carob, guar and tara gums, and predicting the guar content in binary carob-guar mixtures of different geographical origin and harvested in different years. The classification and prediction models are constructed by using linear discriminant analysis (LDA) and multiple linear regression (MLR), respectively. An excellent resolution between the three categories is obtained with LDA, the model being capable of classifying samples with recognition and prediction capabilities of 100%. For MLR models constructed with carob-guar mixtures with and without a common history, the average of the calibration residuals are +/- 0.50 and +/- 0.90%, respectively (average values for the 2-20% guar range). For the later model, the detection limit was 3.2% guar (from the standard deviation of 18 mixtures with 2-4% guar, and for alpha = beta = 0.05).     

Sedimentation of titanium dioxide suspension in the presence of polyacrylamide flocculants

The kinetics of sedimentation of titanium dioxide suspension in aqueous and water-salt media is studied in the presence of high-molecular-weight flocculants — polyacrylamide and ionic (anionic and cationic) acrylamide copolymers. Data are obtained on the influence of flocculant concentration, the chemical nature of repeating units in polymer chains of acrylamide (co)polymers, and the order of the addition of active components on the sedimentation characteristics of titanium dioxide suspension.     

Unique properties of high viscosity gums

Guar gum, a galactomannan from the seed endosperm of the legume, Cyamopsis tetragonolobus, is an important food stabilizer used in a variety of food products ranging from sauces to ice cream. Two guars having viscosities 13-250% higher than conventional guars were studied. Viscosity, effect of shear rate on viscosity, synergy with xanthan gum, granulation, galactomannan content, molecular weight, and scanning electron microscopy of the guar types were evaluated. At equal usage levels of guar, the high viscosity type showed a higher viscosity alone and in combination with xanthan gum under all conditions tested. The high viscosity products have electron microscopic morphology that is more elongated and molecular weights which are greater than normal guars. These factors are discussed in light of the viscosity differences which exist between these products.     

Study on the cationic modification and dyeing of ramie fiber

A modification procedure for ramie fiber using 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC) as a cationic agent and NaOH as a catalyst was developed in this paper. The morphological and structural transformations of the fiber induced by modification were determined by XRD (XRD), differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). XRD results show that the crystal structure of the modified fiber was still preserved although its crystallinity was decreased, which was confirmed from the TGA results. The mechanisms for the modification and dyeing of ramie fiber were analyzed, and the optimum modification conditions were determined to be the CHPTAC concentration of 30 g L⁻¹, the NaOH concentration of 15 g L⁻¹, the reaction temperature of 50 °C, and the reaction time of 60 min. The raw and the modified fibers were dyed with C.I. reactive red 2. The K/S values for the cationic modified fiber increased to be three times as high as the unmodified fiber. The dye uptakes increased greatly with an increase in the nitrogen contents up to 0.4% on the modified fibers.     

Selective chemical modifications of dextran

Specific modification of the reducing end group of dextran has been achieved using the reductive amination procedure and solvent systems designed to optimize polymer reactivity. Dextran fraction (with M _w ranging from 10,000 to 500,000 daltons) were derivatized with [¹⁴C]-octadecylamine in yields of up to 60% to afford the corresponding alkyl dextrans which are of interest as affinity ligands. Reactive dextran intermediates with terminal amine, carboxyl, and aldehyde functions were prepared using sodium cyanoborohydride and ammonium acetate, glycine, and glucosamine, respectively. The dextran glucosamine derivative was further modified by reductive amination with octadecylamine. Similarly, condensation of dextran with streptomycin produced a new type of cationic derivative bearing a terminal, branched saccharide residue. Other reducing-end modifications included nitroxide-spin labelling, covalent attachment to aminopropyl-activated glass beads, and a carbodiimide-mediated amidation of carboxyl—dextran. The reductive amination method was also applied to guar gum and locust bean gum.     

Clarification of kaolin suspension and turbid natural water in the presence of Praestols and aluminum sulfate and aluminosilicate coagulants

The kinetics of clarification of a kaolin suspension and turbid natural water in the presence of coagulants (aluminum sulfate and aluminosilicate) and flocculants (nonionic, cationic, and anionic Praestols) was studied in relation to the concentrations of coagulants and flocculants.     

pH-enzyme di-dependent chronotherapeutic drug delivery system of theophylline for nocturnal asthma

The purpose of this research work was to develop and evaluate a chronotherapeutic based colon-targeted drug delivery system of theophylline (THEO) exploiting pH-enzyme sensitive property for the prevention of episodic attack of asthma in early morning. Guar gum microspheres of theophylline were prepared by emulsification technique. Coating of microspheres was performed using solvent evaporation method with pH sensitive Eudragit(?) polymers. The particle size and surface morphology, entrapment efficiency and degree of swelling of microspheres were examined. The in vitro drug release studies were performed in pH progression medium and also in the presence of 2% rat caecal content. Theophylline was efficiently microencapsulated in guar gum microspheres at different polymer concentrations (1-4%). Fourier transform infrared (FT-IR)-spectroscopy confirmed the intermolecular interactions between guar gum and glutaraldehyde. Coating of guar gum microspheres by Eudragit led to decelerate the in vitro drug release of THEO. Moreover in vitro drug release studies also performed with 2% rat caecal content showed marked increment in drug release. The controlled release of THEO after a lag time was achieved with developed formulation for chronotherapeutic delivery. The pH dependent solubility behavior of Eudragit and gelling properties of guar gum are found to be responsible for delaying the release.