History of Polymer Education-USA

Prior to 1940 there was little or no education directed toward polymer chemistry. With the contributions of Carothers and others that transformed the practice of polymers into a science-and the leadership of Herman Mark and others in formal graduate and postgraduate education-polymer education took root but rapid expansion and general acceptance by more traditionally oriented academic institutions was slowed by many barriers. Only since 1974 has there been a concerted effort to include education in the basic concepts of polymer chemistry into the undergraduate curriculum. Emphasis is on the development of polymer education in the United States.     

Coexistence of multiple conformations in cysteamine monolayers on Au(111)

The structural organization, catalytic function, and electronic properties of cysteamine monolayers on Au(111) have been addressed comprehensively by voltammetry, in situ scanning tunneling microscopy (STM) in anaerobic environment, and a priori molecular dynamics (MD) simulation and STM image simulation. Two sets of voltammetric signals are observed. One peak at -(0.65-0.70) V (SCE) is caused by reductive desorption of cysteamine. The other signal, at -(0.25-0.40) V consists of a peak doublet. The pH dependence of the latter suggests that the origin is catalytic dihydrogen evolution. The doublet feature is indicative of two distinct cysteamine configurations. Cysteamine monolayer formation from initial nucleation to a highly ordered phase has been successfully observed in real time using oxygen-free in situ STM. Random cellular patterns, disordered adlayer formation accompanied by high step edge mobility, and ultimately a highly ordered (square root 3 x 4) R30 degrees lattice are observed sequentially. Pits are formed due to enclosure of the mobile edges during the adsorption process. In the highly ordered cysteamine layer, each unit has two spots with apparent 0.6 A height difference in STM images. The coverage 5.7 +/- 0.1 x 10(-10) mol cm(-2) determined by voltammetry supports that the spots represent two individual cysteamine molecules. A priori MD and density functional simulations hold other clues to the image interpretation and indicate that the NH(3)(+) groups dominate the tunneling contrast. A wide range of interface structures, showing variations in the sulfur binding site and orientation, gauche and trans conformers, and especially hydrogen-bonding interactions, are examined, from which it is concluded that the adsorbate structure is controlled by interactions with the solvent rather than with the substrate.     

The structure,thermodynamic properties and infrared spectra of liquid water and ice

Monte Carlo simulations are used, together with models of the intramolecular and intermolecular potential surfaces, to model liquid water and several phases of ice. Intramolecular relaxation makes important contributions to both thermodynamic and structural properties. A quantum local mode analysis of the Monte Carlo configurations is used to predict the density of states and infrared absorption intensities for the intramolecular bending and stretching vibrations. The large shifts from the gas phase OH stretch frequencies observed experimentally in the liquid and solid phases are due to anharmonic terms in the intramolecular surface rather than to harmonic intermolecular coupling. A significant contribution to observed changes in IR intensity on condensation arises from the large molecular polarisability.     

Density-functional geometry optimization of the 150,000-atom photosystem-I trimer

We present a linear-scaling method based on the use of density-functional theory (DFT) for the system-wide optimization of x-ray structural coordinates and apply it to optimize the 150,000 atoms of the photosystem-I (PS-I) trimer. The method is based on repetitive applications of a multilevel ONIOM procedure using the PW916-31G(d) DFT calculations for the high level and PM3 for the lower level; this method treats all atoms in the structure equivalently, a structure in which the majority of the atoms can be considered as part of some internal "active site." To obtain a realistic single structure, some changes to the original protein model were necessary but these are kept to a minimum in order that the optimized structure most closely resembles the original x-ray one. Optimization has profound effects on the perceived electronic properties of the cofactors, with, e.g., optimization lowering the internal energy of the chlorophylls by on average 53 kcal mol(-1) and eliminates the enormous 115 kcal mol(-1) energy spread depicted by the original x-ray heavy-atom coordinates. A highly precise structure for PS-I results that is suitable for analysis of device function. Significant qualitative features of the structure are also improved such as correction of an error in the stereochemistry of one of the chlorophylls in the "special pair" of the reaction center, as well as the replacement of a water molecule with a metal cation in a critical region on the C3 axis. The method also reveals other unusual features of the structure, leading both to suggestions concerning device functionality and possible mutations between gene sequencing and x-ray structure determination. The optimization scheme is thus shown to augment the molecular modeling schemes that are currently used to add medium-resolution structural information to the raw scattering data in order to obtain atomically resolved structures. System-wide optimization is now a feasible process and its use within protein x-ray data refinement should be considered.