Search

Nanofiltrationmembranes were surface modified by grafting poly(acrylic acid) (PAA)nanochains using a UV initiated free radical polymerization method.These pH sensitive membranes were then used to separate monosaccharides,disaccharides, and their mixtures from filtration feed streams. Itwas found that pH dramatically affects the flux, rejection, and selectivityusing these modified pH sensitive nanofiltration membranes. Membraneperformance could be enhanced not only by the conformational changesof the grafted surface layer due to protonation and deprotonationof the acid groups on the polymer chains but also from the differentinteractions between the sugar molecules and the neutral PAA chainor its negative conjugate. Classical molecular dynamics (MD) simulationswere conducted to investigate the specific interactions between glucose/sucroseand the neutral/negatively charged PAA chains. The simulation resultsshow that both sugar size and PAA charge affect significantly thesugar-polymer interactions. [ABSTRACT FROM AUTHOR]

A bisphosphonate derived ligand was successfully synthesized and grafted from the surface of regenerated cellulose membrane using atom transfer radical polymerization (ATRP) for protein separations. This ligand has a remarkable affinity for arginine (Arg) residues on protein surface. Hydrophilic residues N-(2-hydroxypropyl) methacrylamide (HPMA) was copolymerized to enhance the flexibility of the copolymer ligand and further improve specific protein adsorption. The polymerization of bisphosphonate derivatives was successful for the first time using ATRP. Static and dynamic binding capacities were determined for binding and elution of Arg rich lysozyme. The interaction mechanism between the copolymer ligand and lysozyme was elucidated using classical molecular dynamics (MD) simulations.

Classical molecular dynamics (MD) simulations were conducted for PNIPAM in 1 M monovalent alkali chloride salt solutions as well as in 0.5 M divalent Mg(2+) and Ca(2+) chloride salt solutions. It was found that the strength for the direct alkali ion-amide O binding is strongly correlated with the size of the ionic radius. The smallest Li(+) ion binds strongest to amide O, and the largest Cs(+) ion has the weakest interaction with the amide bond. For the divalent Mg(2+) and Ca(2+) ions, their interactions with the amide bond are weak and appear to be mediated by the water molecules, particularly in the case of Mg(2+), resulting from their strong hydration. The direct binding between the cations and amide O requires partial desovlation of the ions that is energetically unfavorable for Mg(2+) and also to a great extent for Ca(2+). The higher cation charge makes the electrostatic interaction more favorable but the dehydration process less favorable. This competition between electrostatic interaction and the dehydration process largely dictates whether the direct binding between the cation and amide O is energetically preferred or not. For monovalent alkali ions, it is energetically preferred to bind directly with the amide O. Moreover, Li(+) ion is also found to associate strongly with the hydrophobic residues on PNIPAM.

Classical molecular dynamics simulations were performed to investigate the effects of salt on the lower critical solution temperature (LCST) of Poly (N-isopropylacrylamide) (PNIPAM). PNIPAM is often studied as a protein proxy due to the presence of a peptide bond in its monomer unit. PNIPAM is a temperature sensitive polymer which exhibits hydrophobic-hydrophilic phase transition at its LCST. The presence of salt in the solution will shift its LCST, typically to a lower temperature. This LCST shift follows the so-called Hofmeister series. Molecular dynamics (MD) simulations of PNIPAM in 1 M of NaCl, NaBr, NaI, and KCl were carried out to elucidate the effects of different salt on LCST and protein stability. Our results suggest that direct interactions between the salt cations and the polymer play a critical role in the shift of LCST and subsequently on protein stability. Further, cations have a much stronger affinity with the polymer, whereas anions bind weakly with the polymer. Moreover, the cation-polymer binding affinity is inversely correlated with the cation-anion contact pair association constant in solution.

In this study, the kinetics of vesicle formation of ABA amphiphilic triblock copolymers from an initially homogeneous state was theoretically and experimentally investigated by adding a selective solvent into the system. The pathway of spontaneous vesicle formation depended greatly on the selective solvent addition rate. At a slow addition rate, the pathway followed three stages: (1) the amphiphilic triblock copolymer combined into a large irregular aggregation; (2) the large irregular aggregation broke into big irregular spheres; and (3) some hydrophilic molecules in the big irregular spheres diffused toward the surface, and some hydrophilic molecules diffused toward the center, forming vesicles. However, at a fast addition rate, the pathway was as follows: (1) the amphiphilic triblock copolymer aggregated into many small spheres; (2) the small spheres merged to form rod-like micelles first and then oblate membranes; and (3) the oblate membranes closed up to form vesicles. This pathway difference for vesicle formation can be attributed to the existence of many metastable states in the system. This finding not only provides new insight into the origins of vesicles but also provides further understanding on the self-assembly kinetics of amphiphilic block copolymers in a selective solvent.

The effects of ring substitution on the pK(a) value of benzenesulfonic acid (BSA) were investigated using a combined quantum mechanical and classical approach. Ring substitution with strong electron-withdrawing elements such as F, Cl, and Br is found to enhance the acidity of the BSA. More importantly, ring substitution with -NO(2) groups which form an extended conjugated pi-system with the benzene ring exhibits the strongest enhancement of the acidity. The effects of polymerization on the styrenesulfonic acid (SSA) were also investigated by solving the classical Poisson-Boltzmann equation. It is found that polymerization significantly decreases the acidity of SSA due to the alteration of the electrostatic environment surrounding the acid group upon polymerization. The average pK(a) value converges to 2.9 from the corresponding monomer value of -0.53 at a degree of polymerization of 8-12. These results shed significant light on how to design sulfonic-acid-based solid acid catalysts to achieve desired catalytic properties.

The acidity constant pKa for polymeric organic acid is expected to be different from its corresponding monomer value due to the change of chemical environment upon polymerization. Thermodynamic cycles were used to determine the free-energy changes for the proton dissociation processes in aqueous solution and the corresponding pKa values for monomer methacrylic acid and several similar carboxylic acids. First-principles calculations and continuum solvation model were used to determine the gas-phase and solvation free energies, respectively. A protocol was developed to use the efficient density functional calculations with B3LYP functional instead of the demanding CBS-QB3 method to determine the gas-phase free energies with relative high accuracy, thus enabling the determination of pKa values for the short oligomers of methacrylic acid. The predicted pKa values for the dimer and trimer of methacrylic acid are higher by about 0.8 pKa units than the predicted monomer value.

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.