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Full-Text Articles in Physical Chemistry

Particulate Pictures And Kinetic-Molecular Theory Concepts: Seizing An Opportunity, Mark Waner Aug 2010

Particulate Pictures And Kinetic-Molecular Theory Concepts: Seizing An Opportunity, Mark Waner

Mark J. Waner

This work examines commonly used particulate-level pictures meant to illustrate gases. These pictures are found throughout textbooks in the middle grades through the college level, as well as in questions frequently used to assess conceptual learning in students. This work uses the kinetic-molecular theory of gases to demonstrate the inaccuracies often present in these figures, which offers the opportunity to address model limitations to students and to develop better pictures. A basis for using these pictures to discuss models and ideas for ways these pictures can be used for inquiry activities based on analysis of scales is also discussed.


Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner Aug 2010

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner

Mark J. Waner

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …


Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Mark Waner, Michael Nichols Dec 2009

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Mark Waner, Michael Nichols

Mark J. Waner

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …


Imaging The Molecular Dimensions And Oligomerization Of Proteins At Liquid/Solid Interfaces, Mark Waner, Martha Gilchrist, Melvin Schindler, Marcos Dantus Feb 1998

Imaging The Molecular Dimensions And Oligomerization Of Proteins At Liquid/Solid Interfaces, Mark Waner, Martha Gilchrist, Melvin Schindler, Marcos Dantus

Mark J. Waner

Individual Concanavalin A (ConA) molecules have been imaged at the liquid/solid interface with an atomic force microscope (AFM). Three-dimensional sizing with very high resolution (<5 Å) has been obtained by a novel approach based on height distributions, which avoids the tip convolution effects which normally affect scanning probe microscopy techniques. Each height measurement correlates to a particular molecular orientation on the surface. A large number of such measurements provide a statistical ensemble of orientations. The complete height distribution reflects the three-dimensional size of the protein sample and hence its tertiary and quaternary structure. A surface adsorption and orientation model, based on a minimization of surface adsorption energy, is proposed. This model is in good agreement with the observed height distribution of Con A molecules at the liquid/solid interface. Analysis of Con A and succinylated Con A molecules on mica demonstrates that Con A dimers are the prevalent species at the liquid/solid interface. This is in contrast to the tetrameric organization of Con A normally observed in solution. The new possibilities opened by height distribution analysis on the physical characterization of biomolecules at interfaces are also discussed.