Self-consistent effective local potentials

An effective local potential (ELP) is a multiplicative operator whose deviation from a given nonlocal potential has the smallest variance evaluated with a prescribed single-determinant wave function. ELPs are useful in density functional theory as alternatives to optimized effective potentials (OEPs) because they do not require special treatment in finite basis set calculations as OEPs do. We generalize the idea of variance-minimizing potentials by introducing the concept of a self-consistent ELP (SCELP), a local potential whose deviation from its nonlocal counterpart has the smallest variance in terms of its own Kohn-Sham orbitals. A semi-analytical method for computing SCELPs is presented. The OEP, ELP, and SCELP techniques are applied to the exact-exchange-only Kohn-Sham problem and are found to produce similar results for many-electron atoms.     

The effective local potential method: implementation for molecules and relation to approximate optimized effective potential techniques

We have recently formulated a new approach, named the effective local potential (ELP) method, for calculating local exchange-correlation potentials for orbital-dependent functionals based on minimizing the variance of the difference between a given nonlocal potential and its desired local counterpart [V. N. Staroverov et al., J. Chem. Phys. 125, 081104 (2006)]. Here we show that under a mildly simplifying assumption of frozen molecular orbitals, the equation defining the ELP has a unique analytic solution which is identical with the expression arising in the localized Hartree-Fock (LHF) and common energy denominator approximations (CEDA) to the optimized effective potential. The ELP procedure differs from the CEDA and LHF in that it yields the target potential as an expansion in auxiliary basis functions. We report extensive calculations of atomic and molecular properties using the frozen-orbital ELP method and its iterative generalization to prove that ELP results agree with the corresponding LHF and CEDA values, as they should. Finally, we make the case for extending the iterative frozen-orbital ELP method to full orbital relaxation.     

Self-assembly of a cyclobutane beta-tetrapeptide to form nanosized structures

A beta-tetrapeptide made up of homochiral cyclobutane residues displays conformational bias in solution prompted by the formation of intramolecular hydrogen bonds. Moreover, this compound self-assembles to produce nanosized fibrils and, in some media, it also forms a gel. The combination of NMR, TEM, AFM, and theoretical calculations has proven to be very useful in obtaining insight into the details of these new structures.     

Structural and electrocatalytic features of Pt/C catalysts fabricated in supercritical carbon dioxide

Pt/carbon black samples fabricated from dimethyl (1,5-cyclooctadiene) platinum(II) in supercritical CO₂ are characterized in relation to possible applications in methanol fuel cell. The problem of precise material characterization is addressed in frames of X-ray diffractometry, transmission electron microscopy, and electrochemical techniques of the true surface area determination. The catalysts with Pt loading of 20–40 wt.% consist of nm-size particles, with the lattice defectiveness dependent on the fabrication mode. To check the effect of support, various types of carbon blacks (Vulcan XC72R and acetylene black AC-1) are used. In contrast to commercial HiSpec catalysts, no pronounced increase of particle size with Pt loading is found. Specific steady-state activity towards methanol oxidation appears to be essentially higher than for commercial catalysts, mostly because the self-poisoning effects are less pronounced. As for poisoning of Pt with organic species (resulting from the ligand of precursor), its effects are demonstrated to be minor after CO or methanol adsorption accompanied by desorption of contaminating by-product.     

Shuttle-mediated drug delivery to the brain

Advances in the field of shuttle-mediated drug delivery have been made in the last decade; however, the treatment of brain disorders still remains a great challenge because of the presence of the blood-brain barrier (BBB), a structure that limits the access of drugs to their site of action in the central nervous system. Several strategies have been proposed to enhance the transport of drugs across the BBB. In this Review, we focus on the vector-mediated approach, in which a drug is coupled to a molecule (shuttle) that has the ability to cross the BBB and deliver the drug to the brain.     

Synthesis of dysideaproline E using organocatalysis

(S)-4,4-Dichloro-3-methylbutanoic acid was prepared in 51% overall yield from commercially available starting materials using an organocatalytic transfer hydrogenation to 4,4-dichloro-3-methylbut-2-enal in the key step. The (S)-dichloro acid was used as an intermediate in the first total synthesis of dysideaproline E and a diastereomer confirming the structure of the natural product.     

Quantum phenomena in gravitational field

The subjects presented here are very different. Their common feature is that they all involve quantum phenomena in a gravitational field: gravitational quantum states of ultracold antihydrogen above a material surface and measuring a gravitational interaction of antihydrogen in AEGIS, a quantum trampoline for ultracold atoms, and a hypothesis on naturally occurring gravitational quantum states, an Eötvös-type experiment with cold neutrons and others. Considering them together, however, we could learn that they have many common points both in physics and in methodology.     

Gangliosides' analysis by MALDI-ion mobility MS

The combination of ion mobility with matrix-assisted laser desorption/ionization allows for the rapid separation and analysis of biomolecules in complex mixtures (such as tissue sections and cellular extracts), as isobaric lipid, peptide, and oligonucleotide molecular ions are pre-separated in the mobility cell before mass analysis. In this study, MALDI-IM MS is used to analyze gangliosides, a class of complex glycosphingolipids that has different degrees of sialylation. Both GD1a and GD1b, structural isomers, were studied to see the effects on gas-phase structure depending upon the localization of the sialic acids. A total ganglioside extract from mouse brain was also analyzed to measure the effectiveness of ion mobility to separate out the different ganglioside species in a complex mixture.     

Some modular relations for the Göllnitz-Gordon functions and Ramanujan’s modular equations

Huang used the methods of Rogers, Watson and Bressoud to derive some new modular relations involving the Göllnitz-Gordon functions. In this paper, using Ramanujan’s modular equations, we present a uniform method to prove these modular relations established by Huang.