The Chemistry of Water Treatment Processes Involving Ozone,Hydrogen Peroxide and Ultraviolet Radiation

Advanced oxidation processes are defined as those which involve the generation of hydroxyl radicals in sufficient quantity to affect water purification. The theoretical and (practical yield of OH from O₃ at high pH, 0₃/H₂0₂, O₃/UV and H₂O₂/UV systems is reviewed. New data is presented which illustrates the importance of direct photolysis in the O₃/UV process, the effect of the H₂0₂:0₃ ratio in the O₃/H₂O₂ process, and the impact of the low extinction coefficient of H₂O₂ in the H₂0₂/UV process.     

Acquired Predator Recognition by Fathead Minnows: Influence of Habitat Characteristics on Survival

In this study we conditioned fathead minnows (Pimephales promelas) to recognize the odor of a perch (Perca flavescens) by exposing them to perch odor coupled with minnow alarm cue. We then staged encounters between the predator and prey in order to assess whether the predator odor training had any effect on survival of the prey. We tested for a survival effect in the presence and absence of shelter. Our results indicate that fish trained with alarm signals to recognize predators gained a survival benefit during staged encounters with a predator and that habitat characteristics influenced the survival of conditioned fish.     

Influence of polymer molecular weight on selected thermodynamic properties of polymer/solvent systems and the application of the UNIFAC theory

The intrinsic viscosities of eleven narrow molecular weight distribution polystyrene samples ranging from number-average molecular weight 1820 to 1 292 000 have been determined in pure solvents of tetrahydrofuran and chloroform with a Ubbelohde No. 1 viscometer at 25°C. By combining the original and modified Fox-Flory viscosity treatments, respectively, with the Flory-Huggins Lattice theory, the interaction parameters were calculated. With the aid of original and modified UNIFAC methods the solvent activity, clustering function of the solvent, and the interaction parameter were computed and compared with the experimental data. It was established that the influence imposed by the polymer molecular weight on the activity of the solvent, the clustering function of solvent, and interaction parameter is insignificant. The modified UNIFAC method satisfactorily predicted the solvent activity as illustrated by previous investigators. However, both UNIFAC methods failed to predict the interaction parameter.     

Cellulose-binding domains: potential for purification of complex proteins

The endoglucanase CenA and the exoglucanase Cex from Cellulomonasfimi each contain a discrete cellulose-binding domain (CBD),at the amino-terminus or carboxyl-terminus respectively. Thegene fragment encoding the CBD can be fused to the gene of aprotein of interest. Using this approach hybrid proteins canbe engineered which bind reversibly to cellulose and exhibitthe biological activity of the protein partner. Alkaline phosphatase(PhoA) from Escherichia coli, and a ß-glucosidase(Abg) from an Agrobacterium sp. are dimeric proteins. The fusionpolypeptides CenA-PhoA and Abg-CBC_cex are sensitive to proteolysisat the junctions between the fusion partners. Proteolysis resultsin a mixture of homo- and heterodimers; these bind to celluloseif one or both of the monomers carry a CBD, e.g. CenA-PhoA/CenA-PhoAand CenA-PhoA/PhoA. CBD fusion polypeptides could be used inthis way to purify polypeptides which associate with the fusionpartner.     

Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film

Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. A two-step reaction was conducted. First, EAA film was activated with PCl₅ at room temperature. Second, the acid chloride was reacted with dansyl cadaverine or a PEG derivative to form a modified film. ATR-FTIR spectroscopy and fluorometry were employed to analyze the modified films after each step. It was found that dichloromethane yielded the highest grafting efficiency, with the dansyl cadaverine penetrating throughout the ATR-FTIR analysis region (∼400 nm) in a few minutes. As the grafting depth increased with time, so did the amount of fluorescence intensity of grafted dansyl cadaverine. ATR-FTIR spectra for PEG grafting indicated that the acid chloride peak decreased with time, while the ester peak increased. However, hydrolysis occurred at later times, consuming the acid chloride groups within the film. A marked decrease of static water contact angle was observed for EAA grafted with PEG99 (PEG that contains 99 ethylene glycol repeat units), almost 40° lower than that of neat EAA (∼99°). For other PEG-grafted films, the surface hydrophilicity was also improved.     

Electrophilic Aromatic Functionalization of Phenolic Photoresist Polymers

Summary Functionalization of both linear poly(4-hydroxystyrene) (PHS) and branched poly(4-hydroxystyrene) (PHS-B) was accomplished via a Reimer-Tiemann electrophilic aromatic substitution reaction. Linear and branched poly(4-hydroxystyrene-co-5-vinylsalicylaldehyde) (pHS/5VSA and pHS-B/5VSA) copolymers were observed to undergo acid-catalyzed, novolac type self-crosslinking. Both the pHS/5VSA and pHS-B/5VSA copolymer systems possessed a lower deep ultra violet microlithographic sensitivity compared to linear PHS when formulated in negative photoresists. The sluggishness of the negative photoresists containing 5-vinylsalicylaldehyde functionalized copolymers was attributed to a combination of resonance stabilization and steric hindrance effects.     

Chemical Defense in the Plant Bug Lopidea robiniae (Uhler)

Secretions from the metathoracic glands (MTG) of the black locust bug, Lopidea robiniae (Uhler) (Heteroptera: Miridae) contained six major compounds, including (E)-2-hexenal, (E)-2-hexen-1-ol, (E)-2-octenal, (E)-2-octen-1-ol (E)-2-heptenal, and (Z)-3-octen-1-ol. Males and females did not differ significantly in the relative compositions of identified compounds. In feeding trials, six bird species [robin (Turdus migratorious), blue jay (Cyanocitta cristata), brown thrasher (Toxostoma rufum), killdeer (Charadrius vociferus), starling (Sturnus vulgaris), and house wren (Troglodytes aedon)] demonstrated feeding aversions towards L. robiniae, implying that black locust bugs are chemically defended. Bugs discharged the liquid contents of their MTG when attacked, thereby producing a strong and distinct odor. Some birds immediately ejected bugs out of their mouth after biting them, suggesting that the MTG secretion was a deterrent.     

The use of electrochemical noise methods (ENM) to study thick, high impedance coatings

Thick, high impedance organic coatings are those class of coatings used to provide corrosion protection to naval vessels, pipelines, gasoline storage tanks, and other large structures such as bridges and plant structures. These coatings, especially the newest generations now being used in practice, can provide exceptional protection and lifetime of performance such that properly and accurately assessing and differentiating among competing coatings is a very difficult task. The standard protocol of salt fog testing (ASTM B117), immersion testing, and outdoor exposure in a corrosive environment with subjective evaluation of a coating's performance durings and after testing, does not adequatcly rank and predict coating lifetimes for new coating systems, especially for the environmentally compliant coating systems such as powder coatings (especially the thick, fusion bonded epoxy (FBE) coatings used for pipelines), two component epoxy and urethane coatings and waterborne coatings. New, objective test methods are desperately needed by users and manufacturers of coatings. A relatively new electrochemical test procedure, electrochemical noise methods (ENM), as developed by Skerry and Eden, has been shown in our laboratory to be very successful in the ranking and prediction of relative coating performance. We have used the method successfully on naval ship coatings, several pipeline coatings and other related systems, and Skerry has used them successfully on industrial maintenance coatings. We have used these methods in conjunction with electrochemical impedance spectroscopy, d.c. resistance measurements and cyclic salt fog testing of the Prohesion^TM type. In our studies of pipeline coatings, we needed to investigate thermal effects because of their extended range of use temperature. In these studies, we have discovered that electrochemical methods can be used for an in situ measurement of the T_g of coatings in electrolyte immersion. Further, the ‘plasticizing’ effect of aqueous electrolyte absorption as well as its relative irreversibility has been shown. For all coatings studied, ENM provided useful, objective, numerical data which rapidly ranks coatings and provides useful information on the relative lifetime prediction of coatings which may provide up to 30 years of service.     

Influence of block lengths and symmetries of block copolymers on phase behavior of polymer A/polymer B/block copolymer ternary blends

Monte Carlo simulations were used to investigate the compatibilizing effects of diblock copolymers in A/B/A-B diblock copolymer ternary blends and triblock copolymers in A/B/triblock copolymer ternary blends, respectively. The volume fraction of homopolymer A was 19% and was the dispersed phase. The simulation results show that diblock copolymers with longer A-blocks are more efficient as compatibilizers, and symmetric triblock copolymers with a shorter middle block length are easily able to bridge each other through the association of the end blocks. This kind of triblock copolymers have relatively high ability to retard phase separation as compatibilizers.