Viscometric studies of starch-g-polyacrylamide composites

Composites of starch-g-polyacrylamide, starch, and polyacrylamide have been prepared by gamma radiation-initiated polymerization of acrylamide in the presence of starch in aqueous medium. The polymerization was studied as a function of the (i) amount of water (ii) monomer concentration, and (iii) total dose. The optimum conditions for maximum conversion of the monomer to homopolymer and graft copolymer have been evaluated. Percentage of grafting of polyacrylamide could not be determined precisely as both the homopolymer and the graft are soluble in common solvents and all attempts to separate the graft from the homopolymer were unsuccessful. However, the formation of the starch-g-polyacrylamide copolymer was confirmed by the turbidimetric studies using acetone as a nonsolvent. The products of polymerization of acrylamide in the presence of starch consisted of unreacted starch, starch-g-polyacrylamide, and polyacrylamide and is referred to as the composite. Acrylamide was also polymerized in the absence of starch using γ-rays as means of initiation and the optimum conditions for maximum conversion of acrylamide to polyacrylamide have been evaluated. Viscosity behavior of the composite and polyacrylamide was studied in aqueous medium at 30±0.04°C. The reduced specific viscosity of the aqueous solution of acrylamide and the composite as well was found to increase with increasing dilution, the effect being more pronounced in the composite. This tends to indicate that both the homopolymer and the composite behave as polyelectrolytes. An attempt has been made to explain the polyelectrolytic behavior of the homopolymer and the composite. © 1993 John Wiley & Sons, Inc.     

Graft copolymerization of acrylonitrile and methacrylonitrile onto gelatin by mutual irradiation method

In order to improve upon certain properties of gelatin graft copolymerization of acrylonitrile (AN) and methacrylonitrile (MAN) onto gelatin has been studied in aqueous medium using γ rays as a source of initiation. Optimum conditions for affording maximum percentage of grafting have been evaluated as a function of various reaction parameters. The grafted polyacrylonitrile (PAN) was isolated from the graft copolymer by acid hydrolysis, and the average molecular weight (M_v) of the isolated polymer has been determined viscometrically. The graft copolymers were characterized by IR spectroscopic methods and thermogravimetric analysis (TGA). Acrylonitrile was found to be more reactive than methacrylonitrile toward graft copolymerization. © 1994 John Wiley & Sons, Inc.     

Failure analysis of air pre-heater tubes of a petrochemicals plant

Heat resistant alloy tubes used in the higher temperature range of 1150–1273 K depends on the protective scale integrity for prevention of corrosion induced premature failures in a mixed gas environment with potential corrodents for oxidation, carburization and sulphidation attack. Cast HK40+Nb alloy tubes of an air pre-heater unit of a petrochemical industry failed prematurely after 13,000 h in service. The unit used smoke gas containing gaseous corrodents that could cause oxidation/sulphidation/carburization type of attack. Failed parts showed crack/punctures below the corrosion product filled pits. The crack occurred in the fully carburized zone present at the thinned out centre of the pit. Factors like excessive temperature cycling, overheating, presence of impurities either in the pre-heating gas mixture or that got introduced while in operation were found to be the reasons for breach of protective scale integrity leading to unwarranted corrosion attack resulting in thinning of tube material and internal corrosion penetration which finally led to premature failure.     

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.     

α-Glucosidase and α-amylase inhibitory constituent of Carex baccans: Bio-assay guided isolation and quantification by validated RP-HPLC–DAD

Carex baccans is used extensively as food additive for its medicinal and nutritional properties. Its extract demonstrated significant inhibition of α-glucosidase and α-amylase with IC₅₀ 43.32 ± 1.22 and 562.18 ± 5.98 μg/mL, respectively. A bio-assay guided approach was employed to identify the active constituent(s). Fractionation and purification of the extract led to the isolation of a potent inhibitor, (+)-α-viniferin, and of weak inhibitors smiglasides A and B. (+)-α-Viniferin was quantified in the extract and fractions using HPLC and the method was validated for linearity, limit of detection, limit of quantification, precision, and accuracy. The calibration curve showed good linearity (r² > 0.999) in the range of 7.813–250 μg/mL. The identification of α-glucosidase and α-amylase inhibitory activity in C. baccans supports the possible use of the plant as functional food for the management of diabetes. The validated HPLC method for the study of plant extracts will be useful in future research.     

Staphylococcus aureus Exfoliative Toxin E,Oligomeric State and Flip of P186: Implications for Its Action Mechanism

Staphylococcal exfoliative toxins (ETs) are glutamyl endopeptidases that specifically cleave the Glu381-Gly382 bond in the ectodomains of desmoglein 1 (Dsg1) via complex action mechanisms. To date, four ETs have been identified in different Staphylococcus aureus strains and ETE is the most recently characterized. The unusual properties of ETs have been attributed to a unique structural feature, i.e., the 180° flip of the carbonyl oxygen (O) of the nonconserved residue 192/186 (ETA/ETE numbering), not conducive to the oxyanion hole formation. We report the crystal structure of ETE determined at 1.61 Å resolution, in which P186(O) adopts two conformations displaying a 180° rotation. This finding, together with free energy calculations, supports the existence of a dynamic transition between the conformations under the tested conditions. Moreover, enzymatic assays showed no significant differences in the esterolytic efficiency of ETE and ETE/P186G, a mutant predicted to possess a functional oxyanion hole, thus downplaying the influence of the flip on the activity. Finally, we observed the formation of ETE homodimers in solution and the predicted homodimeric structure revealed the participation of a characteristic nonconserved loop in the interface and the partial occlusion of the protein active site, suggesting that monomerization is required for enzymatic activity.     

Influence of applied stress ratio on fatigue crack growth in 6063-T6 aluminium alloy

Crack growth data of 6063-T6 sheet material were analysed with different formulas for ΔK_eff as a function of stress ratio R. The data covered R values from 0·1 to 0·5. A good correlation was obtained for $\text{d}\text{a}\text{d}\text{N}$ and ΔK_eff using the Schijve⁶ equation for U.     

A study of crack closure under constant amplitude loading for 6063-T6 Al-alloy

Crack closure experiments were performed on 6063-T6 Al-alloy, using a COD gauge for various load ranges (Δp) and stress ratios, R. On the basis of the experimental results a model for effective stress intensity range ratio U was developed. This model was found to be a function of the stress ratio, R, and was fitted to existing constant amplitude crack propagation data for 6063-T6 Al-alloy. The crack closure load stabilized after 1 mm initial crack growth.     

Effect of stress ratio on effective stress range ratio and crack growth in 6061-T6 Al-alloy

Crack closure experiments using a COD gauge were performed on 6061-T6 Al-alloy, for various stress ratios. Experimental results show that for a given stress ratio, R, the crack length increases up to 1 mm after which it is stabilized. On the basis of the experimental results a model for effective stress range ratio U, which was found to be a function of stress ratio R, was developed. This model was fitted to existing constant amplitude crack propagation data for the 6061-T6 Al-alloy.     

A study of effective stress range ratio in programmed loadings

Crack closure experiments were performed on 6061-T6 and 6063-T6 Al alloys for Lo-Hi and Hi-Lo programmed loadings. In these experiments each block of overload was continued to propagate up to 2 mm crack length. In the Lo-Hi load sequences the closure load increases but the value of U remains the same. The crack growth rate accelerated due to larger value of ΔK. The values of U stabilized in about 10 cycles for each block. In Hi-Lo load sequences, retardation takes place. The closure load increases and becomes stabilized in 10 cycles. It remains constant for a number of cycles and reaches its CAL closure value.