Characterization of the least concave majorant of brownian motion,conditional on a vertex point,with application to construction

The characterization of the least concave majorant of brownian motion by Pitman (1983,Seminar on Stochastic Processes, 1982 (eds. E. Cinlar, K. L. Chung and R. K. Getoor), 219–228, Birkhäuser, Boston) is tweaked, conditional on a vertex point. The joint distribution of this vertex point is derived and is shown to be generated with extreme ease. A procedure is then outlined by which one can construct the least concave majorant of a standard Brownian motion path over any finite, closed subinterval of (0, ∞). This construction is exact in distribution. One can also construct a linearly interpolated version of the Brownian motion path (i.e. we construct the Brownian motion path over a grid of points and linearly interpolate) corresponding to this least concave majorant over the same finite interval. A discussion of how to translate the aforementioned construction to the least concave majorant of a Brownian bridge is also presented.     

Vibrational and correlation effects on properties of water

Large basis set, ab initio potential energy and property surfaces of water have been used with quantum Monte Carlo vibrational analysis in the evaluation of the molecule's rotational constants, zero-point energy, and dipole moment. While there are clearly differences in vibrational state parameters due to including correlation effects, the vibrational averaging effect on rotational constants is very nearly additive with the correlation effect. This has implications for evaluation and estimation of properties of molecules in specific vibrational states. Received: 9 February 1999 / Accepted: 11 February 1999 / Published online: 5 May 1999     

Remarkable features in the interactions of quadrupolar molecules

Quadrupolar charge fields of molecules and of molecular fragments give rise to unique features in weakly interacting clusters and aggregations. Relative to dipole-dipole interactions, the interactions among quadrupolar molecules tend to allow for greater orientational distortions away from equilibrium. Potential surface regions have been found for several clusters that are attractive and yet very flat for certain directions. There is a notable slipperiness for the interactions in some of these cases. This implies significant vibrational excursions even in the ground state. Furthermore, the coupling of rotations among nearby molecules in pure clusters of quadrupolar molecules is different than for dipolar species, and it can lead to unexpectedly small internal rotation barriers. How these and other features develop and what they might imply for materials and biomolecular simulations are discussed here.     

Conformational energetics in hydrogen-bonded dimers. The unobserved CO---HF complex

Ab initio electronic-structure calculations with large basis sets and extensive treatment of electron correlation have been carried out for the CO---HF complex. The potential surface exhibits a local minimum for linear CO---HF that is over 400 cm⁻¹ above the absolute minimum that corresponds to the OC---HF structure. The main reason for the difference in the stabilities of the two conformers is the difference in their electron-correlation energies. The interconversion of CO---HF to OC---HF follows a minimum-energy path that takes the complex through a structure where the fluorine end of HF points into the middle regions of CO.     

An efficient and accurate approximation to double substitution coupled cluster wavefunctions

An approximate CCD theory in an efficient electron pair operator form has been applied to He₂ with very accurate results.     

The potential energy curves of HeBe,HeMg and BeMg

Correlated calculations have been performed on the potential curves of mixed dimers of He, Be and Mg He interacts weakly with all partners. BeMg appears to be intermediate in well-depth to Be₂ and Mg₂ and has electronic structure features similar to Be₂ but different from Mg₂.     

Concise,open-ended implementation of Rys polynomial evaluation of two-Electron integrals

A quadrature-point-driven implementation of the standard Rys polynomial method for computing two-electron repulsion integrals of gaussian basis functions has been found to be both concise and openended with respect to the angular momentum of the gaussian functions (i.e., s,p,d,f,g,…). These are important features in certain applications, such as molecular properties and property gradients.     

Synthetic mimics of small Mammalian cell surface receptors

Receptors on the surface of mammalian cells promote the uptake of cell-impermeable ligands by receptor-mediated endocytosis. To mimic this process, we synthesized small molecules designed to project anti-dinitrophenyl antibody-binding motifs from the surface of living Jurkat lymphocytes. These synthetic receptors comprise N-alkyl derivatives of 3beta-cholesterylamine as the plasma membrane anchor linked to 2,4-dinitrophenyl (DNP) and structurally similar fluorescent 7-nitrobenz-2-oxa-1,3-diazole (NBD) headgroups. Insertion of two beta-alanine subunits between a DNP derivative and 3beta-cholesterylamine yielded a receptor that avidly associates with cell surfaces (cellular t(1/2) approximately 20 h). When added to Jurkat cells at 10 microM, this receptor enhanced uptake of an anti-DNP IgG ligand by approximately 200-fold in magnitude and approximately 400-fold in rate within 4 h (ligand internalization t(1/2) approximately 95 min at 37 degrees C). This non-natural receptor mimics many natural receptors by dynamically cycling between plasma membranes and intracellular endosomes (recycling t(1/2) approximately 3 min), targeting of protein ligands to proposed cholesterol and sphingolipid-enriched lipid raft membrane microdomains, and delivery of protein ligands to late endosomes/lysosomes. Quantitative dithionite quenching of fluorescent extracellular NBD headgroups demonstrated that other 3beta-cholesterylamine derivatives bearing fewer beta-alanines in the linker region or N-acyl derivatives of 3beta-cholesterylamine were less effective receptors due to more extensive trafficking to internal membranes. Synthetic cell surface receptors have potential applications as cellular probes, tools for drug delivery, and methods to deplete therapeutically important extracellular ligands.