LOCAL EQUILIBRIUM THEORY FOR THE DYNAMICS OF NONISOTHERMAL MIXED GAS ADSORPTION OF HIGH-CONCENTRATION COMPONENTS

A local equilibrium theory for nonisothermal gas adsorption is developed which accounts for variations in interstitial gas velocity induced by adsorption. Also presented are expressions describing the entropy admissibility criterion. A solution is developed for a Riemann's problem involving adiabatic gas-phase adsorption where there is no inert diluent and where Langmuir isotherms apply.     

Context dependence of phenotype prediction and diversity in combinatorial mutagenesis

Two different combinatorial mutagenesis experiments on the light-harvestingII (LH2) protein of Rhodobacter capsulatus indicate that heuristicrules relating sequence directly to phenotype are dependenton which sets or groups of residues are mutated simultaneously.Previously reported combinatorial mutagenesis of this chromogenicprotein (based on both phylogenetic and structural models) showedthat substituting amino acids with large molar volumes at Gly^ß31caused the mutated protein to have a spectrum characteristicof light-harvesting I (LH1). The six residues that underwentcombinatorial mutagenesis were modeled to lie on one side ofa transmembrane -helix that binds bacteriochlorophyll. In asecond experiment described here, we have not used structuralmodels or phylogeny in choosing mutagenesis sites. Instead,a set of six contiguous residues was selected for combinatorialmutagenesis. In this latter experiment, the residue substitutedat Gly^ß31 was not a determining factor in whetherLH2 or LH1 spectra were obtained; therefore, we conclude thatthe heuristic rules for phenotype prediction are context dependent.While phenotype prediction is context dependent, the abilityto identify elements of primary structure causing phenotypediversity appears not to be. This strengthens the argument forperforming combinatorial mutagenesis with an arbitrary groupingof residues if structural models are unavailable.     

Organolithium route to poly(arylsilane)s

Various poly(arylsilane)s The poly(carbosilane)s prepared in this way are of higher molecular weight than when prepared by the Wurtz-type condensation route previously reported. TG shows 40–50% overll weight loss attained at 500–600°C.     

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.