Mechanistic Insight into Peptidyl-Cysteine Oxidation by the Copper-Dependent Formylglycine-Generating Enzyme

The copper-dependent formylglycine-generating enzyme (FGE) catalyzes the oxygen-dependent oxidation of specific peptidyl-cysteine residues to formylglycine. Our QM/MM calculations provide a very likely mechanism for this transformation. The reaction starts with dioxygen binding to the tris-thiolate Cu^I center to form a triplet Cu^II-superoxide complex. The rate-determining hydrogen atom abstraction involves a triplet-singlet crossing to form a Cu^II−OOH species that couples with the substrate radical, leading to a Cu^I-alkylperoxo intermediate. This is accompanied by proton transfer from the hydroperoxide to the S atom of the substrate via a nearby water molecule. The subsequent O−O bond cleavage is coupled with the C−S bond breaking that generates the formylglycine and a Cu^II-oxyl complex. Moreover, our results suggest that the aldehyde oxygen of the final product originates from O₂, which will be useful for future experimental work.     

Some Useful Integral Representations for Information-Theoretic Analyses

This work is an extension of our earlier article, where a well-known integral representation of the logarithmic function was explored and was accompanied with demonstrations of its usefulness in obtaining compact, easily-calculable, exact formulas for quantities that involve expectations of the logarithm of a positive random variable. Here, in the same spirit, we derive an exact integral representation (in one or two dimensions) of the moment of a nonnegative random variable, or the sum of such independent random variables, where the moment order is a general positive non-integer real (also known as fractional moments). The proposed formula is applied to a variety of examples with an information-theoretic motivation, and it is shown how it facilitates their numerical evaluations. In particular, when applied to the calculation of a moment of the sum of a large number, n, of nonnegative random variables, it is clear that integration over one or two dimensions, as suggested by our proposed integral representation, is significantly easier than the alternative of integrating over n dimensions, as needed in the direct calculation of the desired moment.     

Improved lower bounds on the total variation distance for the Poisson approximation

New lower bounds on the total variation distance between the distribution of a sum of independent Bernoulli random variables and the Poisson random variable (with the same mean) are derived via the Chen–Stein method. The new bounds rely on a non-trivial modification of the analysis by Barbour and Hall (1984) which surprisingly gives a significant improvement. A use of the new lower bounds is addressed.     

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.     

Salt‐Induced Depression of Lower Critical Solution Temperature in a Surface‐Grafted Neutral Thermoresponsive Polymer

Summary: Quartz crystal microbalance with dissipation monitoring (QCM‐D) is employed to determine the effect of salt on the volume phase transition of thermoresponsive polymer brushes. Changes in mass and viscoelasticity of poly(N‐isopropylacrylamide) (PNIPAM) layers grafted from a QCM‐D crystal are measured as a function of temperature, upon contact with aqueous solutions of varying salt concentrations. The phase‐transition temperature of PNIPAM brushes, T_C,graft, quantified from the QCM‐D measurements is found to decrease as the concentration of salt is increased. This phenomenon is explained by the tendency of salt ions to affect the structure of water molecules (Hofmeister effect). However, in contrast to the linear decrease in phase‐transition temperature upon increasing salt concentration observed for free PNIPAM, the trend in T_C,graft for PNIPAM brushes is distinctively non‐linear.

Schematic representation of the effect of salt concentration on the phase transition behavior of thermoresponsive polymer brushes.