Search results for "Colloid"

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-9…

2013

The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…

Mononuclear rearrangement of heterocycles in zwitterionic micelles of amine oxide surfactants.

2012

Abstract Rate constants for the mononuclear rearrangement (MRH) of Z -phenylhydrazones of some 5-substituted-3-benzoyl-1,2,4-oxadiazoles in water have been measured in the presence of zwitterionic micelles. The use of micellized N -tetradecyl- N , N -dimethylamineoxide (C 14 DMAO) as the reaction medium allowed to solubilize the otherwise water-insoluble oxadiazoles. Micellar rate effects were analyzed by using a simple pseudo-phase model and compared with those obtained in non-ionic micelles (Triton X-100). Evidence that both the rate of the rearrangement reaction and the binding of the substrates to the micelles are mainly governed by substrate hydrophobicity is obtained. The disagreement…

Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C—H Bonds with Stereoretention

2015

An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tande…

Stereocontrol in Diphenylprolinol Silyl Ether Catalyzed Michael Additions : Steric Shielding or Curtin-Hammett Scenario?

2017

The enantioselectivity of amine-catalyzed reactions of aldehydes with electrophiles is often explained by simple steric arguments emphasizing the role of the bulky group of the catalyst that prevents the approach of the electrophile from the more hindered side. This standard steric shielding model has recently been challenged by the discovery of stable downstream intermediates, which appear to be involved in the rate-determining step of the catalytic cycle. The alternative model, referred to as Curtin-Hammett scenario of stereocontrol, assumes that the enantioselectivity is related to the stability and reactivity of downstream intermediates. In our present computational study, we examine th…

Pressure dependent arrangement of a protein in two-dimensional crystals specifically bound to a monolayer

1993

Abstract The arrangement of streptavidin bound to a biotinylated monolayer of a polymeric amphiphile at the air-water interface is studied as a function of lateral pressure or ligand density. Closely packed domains are observed by fluorescence microscopy. The arrangement of the protein in these domains is sensitively detected by X-ray reflectivity and an especially thorough data analysis yields the following: the distance of the protein from the air-monolayer interface varies with lateral pressure by 10 A; the interfaces involving the protein are much rougher than expected due to capillary waves; the electron density of the protein layer increases considerably on compression, which can be u…

Molecular Recognition of Biotinyl Hydrophobic Helical Peptides with Streptavidin at the Air/Water Interface

1994

Bilayer Formation of Streptavidin Bridged by Bis(biotinyl) Peptide at the Air/Water Interface

1994

Confined binary two-dimensional colloidal crystals: Monte Carlo simulation of crack formation.

2010

Binary mixtures (A, B) of colloidal particles of different sizes in two dimensions may form crystals with square lattice structure (the A-particles occupying the white sites and the B-particles the black sites of a checkerboard). Confining such a system by two parallel 'walls' a distance D apart, long-range order in the direction parallel to the walls is stabilized by 'corrugated walls' that are commensurate with the lattice structure but destabilized by structureless 'hard walls', even if there is no misfit between the strip width D and the crystal lattice spacing. The crossover to quasi-one-dimensional behavior is studied by Monte Carlo simulations, analyzing Lindemann parameters and disp…

Negative Interfacial Tension in Phase-Separated Active Brownian Particles.

2015

We study numerically a model for active suspensions of self-propelled repulsive particles, for which a stable phase separation into a dilute and a dense phase is observed. We exploit the fact that for nonsquare boxes a stable "slab" configuration is reached, in which interfaces align with the shorter box edge. Evaluating a recent proposal for an intensive active swimming pressure, we demonstrate that the excess stress within the interface separating both phases is negative. The occurrence of a negative tension together with stable phase separation is a genuine nonequilibrium effect that is rationalized in terms of a positive stiffness, the estimate of which agrees excellently with the numer…

Interplay of three G‑quadruplex units in the KIT promoter

2019

The proto-oncogene KIT encodes for a tyrosine kinase receptor, which is a clinically validated target for treating gastrointestinal stromal tumors. The KIT promoter contains a G-rich domain within a relatively long sequence potentially able to form three adjacent G-quadruplex (G4) units, namely, K2, SP, and K1. These G4 domains have been studied mainly as single quadruplex units derived from short truncated sequences and are currently considered promising targets for anticancer drugs, alternatively to the encoded protein. Nevertheless, the information reported so far does not contemplate the interplay between those neighboring G4s in the context of the whole promoter, possibly thwarting dru…