SPECTROSCOPY AND FLUORESCENCE QUENCHING OF TYROSINE IN LIMA BEAN TRYPSIN/CHYMOTRYPSIN INHIBITOR AND MODEL PEPTIDES

The effects of citrate ion concentration and pH on the optical spectra and fluorescence decay have been measured for several tyrosine model compounds and lima bean trypsin/chymotrypsin inhibitor, a protein containing one tyrosine at position 69 and seven disulfides but no tryptophan, in order to determine the location and environment of Tyr 69. Tyrosine in the protein is protected from citrate collisional quenching, as indicated by the dynamic quenching constant 9 to 15 times smaller than those for the model peptides. Static quenching remains, with a Stern-Volmer constant of about 1.0 M-1, somewhat smaller than those of L-tyrosine, tyrosine-glutamate, and leucine-tyrosine-leucine. The elevated pKa of Tyr 69, greater than or equal to 11.6, also indicates protein protection from solvent ions. Though Coulomb repulsion of the Glu 70/citrate pair may play a role in the shielding of Tyr 69 from citrate, our measurements indicate that steric effects of the protein structure are more important. Tyrosinate emission in the protein at neutral pH is minimal.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

Nondislocation origin of GaAs nanoindentation pop-in event

The present Letter demonstrates a pop-in event that is caused by a nanoindentation-induced phase transformation in GaAs, and not accompanied by any dislocation nucleation. Our computer simulations reveal the appearance of the new phase, documented by the structural correlation functions and visualization of the atomic positions. This challenges the orthodox view that the initial pop-in event reflects nucleation of dislocations or their movement, and has a bearing on materials where dislocation activity is not present.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts

Ni,N‐doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen‐coordinated, single Ni atom active sites. However, experimentally confirming Ni?N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile‐derived Ni,N‐doped carbon electrocatalysts (Ni‐PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X‐ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square‐planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

Supersonic turbulence and structure of interstellar molecular clouds

The interstellar medium provides a unique laboratory for highly supersonic, driven hydrodynamic turbulence. We propose a theory of such turbulence, test it by numerical simulations, and use the results to explain observational scaling properties of interstellar molecular clouds, the regions where stars are born.     

Ultrafast molecular dissociation of water in ice

Using x-ray emission and photoemission spectroscopies to measure the occupied valence levels in a thin crystalline ice film, we resolve the ionization-induced dissociation of water in ice on a femtosecond time scale. Isotope substitution confirms proton transfer during the core-hole lifetime in spite of the nonresonant excitation. Through ab initio molecular dynamics on the core-ionized state, the dissociation and spectrum evolution are followed at femtosecond intervals. The theoretical simulations confirm the experimental analysis and allow for a detailed study of the dissociative reaction path.     

LP formulations of the shortest path tree problem

Based on a pair of primal-dual LP formulations of the shortest path tree problem, the first algorithmic approach to reoptimizing the shortest paths subject to changes in the edge weights was proposed by S. Pallottino and M.G. Scutellá in 2003. We shall here focus solely on their introductory sections, propose some simplifications of the models considered, and finally relate the resulting models to the presentation of single-source shortest path problems in textbooks treating this subject with but limited or no reference to LP.Received: April 2004, Revised: August 2004, MSC classification: 90C05, 90C35, 90B10 Dedicated to the memory of Stefano Pallottino     

Hillock formation on ion-irradiated graphite surfaces

Abstract

Scanning probe microscopy experiments show that ion irradiation of (0001) graphite results in the formation of isolated defects comprising of a few tens of atoms. We use molecular dynamics simulations and density-functional theory calculations to study the formation probabilities of these defects. We identify different defect structures which correspond to experimentally observed hillocks on graphite surfaces. We find that the predominant source of defects are vacancies and interlayer interstitials, and identify a three-atom carbon ring defect on the graphite surface.     

Increasing correlation length in bulk supercooled H2O, D2O, and NaCl solution determined from small angle x-ray scattering

Using small angle x-ray scattering, we find that the correlation length of bulk liquid water shows a steep increase as temperature decreases at subzero temperatures (supercooling) and that it can, similar to the thermodynamic response functions, be fitted to a power law. This indicates that the anomalous properties of water are attributable to fluctuations between low- and high-density regions with rapidly growing average size upon supercooling. The substitution of H(2)O with D(2)O, as well as the addition of NaCl salt, leads to substantial changes of the power law behavior of the correlation length. Our results are consistent with the proposed existence of a liquid-liquid critical point in the deeply supercooled region but do not exclude a singularity-free model.