Intermediate structure of the giant dipole resonance in 54Fe and 56Fe

The cross sections for the (γ, n) reaction on ⁵⁴Fe and ⁵⁶Fe for the high-energy component of the neutron spectrum have been investigated using a neutron spectrometer and a synchrotron with a photon energy range from 5 to 26.3 MeV. Neutron energy spectra have been measured. It is shown that the intermediate structure in the (γ, n) reaction cross section is due to high-energy neutrons and correlates with the structure in the neutron spectrum.     

Horocycle flows are loosely Bernoulli

It is proved that horocycle flows associated with transitiveC ²-Anosov flows are loosely Bernoulli with respect to their unique ergodic measures. Partially supported by the Sloan Foundation and NSF Grant MCS74-19388.     

Application of a screened INDO model (INDO/S) to spectroscopic properties of TCNQ and its anions

Theoretical Chemistry Accounts - An INDO model Hamiltonian, incorporating screening within the π-system and parametrized particularly to describe dynamical properties (photoemission and...     

First-order model potential for optical dipole transitions: Application to the lithium isoelectronic sequence

We have constructed two first-order model potentials which were designed to yield dipole transition moments, and have applied them to the lithium isoelectronic sequence. The models contain two or three adjustable parameters, chosen so as to reproduce selected transition moment data on a single ion of the sequence. With negligible computational effort, they both yield other transition moments of high accuracy.     

Erratum to “The primes contain arbitrarily long polynomial progressions”

In our previous paper “The primes contain arbitrarily long polynomial progressions” [Acta Math., 201 (2008), 213–305] there were some minor errors in our definition of the polynomial forms and polynomial correlation conditions, which is unreasonably strong as written due to the overly loose bound on the degree of the polynomials involved. In this erratum we repair this issue by capping the degree of the polynomials more strongly, and adjusting some other relevant components of the argument accordingly.     

Water perturbed by cellophane: comparison of its physicochemical properties with those of water perturbed with cotton wool or Nafion

We present experimental data on water repetitively brought in contact with cellophane. Although this hydrophilic polymer is insoluble in water, repetitively immersing it in water changes the liquid’s properties. We compare the physicochemical properties of the water left over after removing the cellophane to those of previously published data on water repetitively brought in contact with other in water insoluble polymers (cotton wool or Nafion). Some of the properties are similar. All the properties considerably differ from those of the Milli-Q^® water used. On lyophilizing these waters, solid residues remain. The residues are soluble in water. The chemical nature of the residues differs from that of the perturbing polymers.

     

DNA polymerase beta catalysis: are different mechanisms possible?

DNA polymerases are crucial constituents of the complex cellular machinery for replicating and repairing DNA. Discerning mechanistic pathways of DNA polymerase on the atomic level is important for revealing the origin of fidelity discrimination. Mammalian DNA polymerase beta (pol beta), a small (39 kDa) member of the X-family, represents an excellent model system to investigate polymerase mechanisms. Here, we explore several feasible low-energy pathways of the nucleotide transfer reaction of pol beta for correct (according to Watson-Crick hydrogen bonding) G:C basepairing versus the incorrect G:G case within a consistent theoretical framework. We use mixed quantum mechanics/molecular mechanics (QM/MM) techniques in a constrained energy minimization protocol to effectively model not only the reactive core but also the influence of the rest of the enzymatic environment and explicit solvent on the reaction. The postulated pathways involve initial proton abstraction from the terminal DNA primer O3'H group, nucleophilic attack that extends the DNA primer chain, and elimination of pyrophosphate. In particular, we analyze several possible routes for the initial deprotonation step: (i) direct transfer to a phosphate oxygen O(Palpha) of the incoming nucleotide, (ii) direct transfer to an active site Asp group, and (iii) transfer to explicit water molecules. We find that the most probable initial step corresponds to step (iii), involving initial deprotonation to water, which is followed by proton migration to active site Asp residues, and finally to the leaving pyrophosphate group, with an activation energy of about 15 kcal/mol. We argue that initial deprotonation steps (i) and (ii) are less likely as they are at least 7 and 11 kcal/mol, respectively, higher in energy. Overall, the rate-determining step for both the correct and the incorrect nucleotide cases is the initial deprotonation in concert with nucleophilic attack at the phosphate center; however, the activation energy we obtain for the mismatched G:G case is 5 kcal/mol higher than that of the matched G:C complex, due to active site structural distortions. Taken together, our results support other reported mechanisms and help define a framework for interpreting nucleotide specificity differences across polymerase families, in terms of the concept of active site preorganization or the so-called "pre-chemistry avenue".