The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements,adsorption isotherm determination,and FT Raman characterization

The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.     

CO Oxidation Catalytic Effects of Intrinsic Surface Defects in Rhombohedral LaMnO3

There is an ongoing effort to replace rare and expensive noble-element catalysts with more abundant and less expensive transition metal oxides. With this goal in mind, the intrinsic defects of a rhombohedral perovskite-like structure of LaMnO₃ and their implications on CO catalytic properties were studied. Surface thermodynamic stability as a function of pressure (P) and temperature (T) were calculated to find the most stable surface under reaction conditions (P=0.2 atm, T=323 K to 673 K). Crystallographic planes (100), (111), (110), and (211) were evaluated and it was found that (110) with MnO₂ termination was the most stable under reaction conditions. Adsorption energies of O₂ and CO on (110) as well as the effect of intrinsic defects such as Mn and O vacancies were also calculated. It was found that O vacancies favor the interaction of CO on the surface, whereas Mn vacancies can favor the formation of carbonate species.     

Predicting crystal structures with data mining of quantum calculations

Predicting and characterizing the crystal structure of materials is a key problem in materials research and development. It is typically addressed with highly accurate quantum mechanical computations on a small set of candidate structures, or with empirical rules that have been extracted from a large amount of experimental information, but have limited predictive power. In this Letter, we transfer the concept of heuristic rule extraction to a large library of ab initio calculated information, and we demonstrate that this can be developed into a tool for crystal structure prediction.     

Investigation of endoglucanase selectivity on carboxymethyl cellulose by mass spectrometric techniques

The benefits of applying cellulose selective enzymes as analytical tools for chemical structure characterization of cellulose derivatives have been frequently addressed over the years. In a recent study the high selectivity of cellulase Cel45A from Trichoderma reesei (Tr Cel45A) was utilized for relating the chemical structure to the flow properties of carboxymethyl cellulose (CMC). However, in order to take full advantage of the enzymatic hydrolysis the enzyme selectivity on the cellulose substrate must be further investigated. Therefore, the selectivity of Tr Cel45A on CMC was studied by chemical sample preparation of the enzyme products followed by mass spectrometric chemical structure characterization. The results strongly suggest that, in accordance with recent studies, also this highly selective endoglucanase is able to catalyze hydrolysis of glucosidic bonds adjacent to mono-substituted anhydroglucose units (AGUs). Furthermore, the results also indicate that substituents on the nearby AGUs will affect the hydrolysis.     

Resonant dynamics in a rotordynamic system with nonlinear inertial coupling and shaft anisotropy

The response of a nonlinear, damped Jeffcott rotor with anisotropic stiffness is considered in the presence of an imbalance. For sufficiently small external torque or large imbalance, resonance capture or rotordynamic stall can occur, whereby the rotational velocity of the shaft is unable to increase beyond the fundamental resonance between the rotational and translational motion. This phenomena provides a mechanism for energy transfer from the rotational to the translational mode. Using the method of averaging a reduced-order model is developed, valid near the resonance, that describes this resonant behavior. The equilibrium points of these averaged equations, which correspond to stationary solutions of the original equations and rotordynamic stall, are described as the applied torque, damping, and anisotropy vary. As the anisotropy increases, assumed to arise from increasing shaft cracks, the torque required to eliminate the possibility of stall increases. However, when the system is started with zero initial conditions, the minimum torque required to pass through the resonance is approximately constant as the anisotropy increases. The predictions from the reduced-order model are verified against numerical simulations of the original equations of motion.