A chiral A2 B2 macrocyclic minireceptor with extreme enantioselectivity

We describe a novel macrocyclic minireceptor that is assembled from a chiral 1,2-diamine and 5-allyloxyisophthalic acid. After immobilization on HPLC silica, the chiral macrocycle preferentially binds the L-enantiomers of simple amino acid derivatives, with enantioselectivities values up to 3.0 kcal/mol. [structure: see text]     

Semiempirical evaluation for proton affinities of phosphorus compounds

We here report the AM 1 and PM 3 evaluation of proton affinities for phosphorus compounds. The substituent effects, the preferred site of protonation, and the geometry changes produced upon protonation are discussed in terms of the present semiempirical calculations that are compared with experimental data and previous ab initio results. © 1993 John Wiley & Sons, Inc.     

The Role of Spin in Entanglement Generated by Expanding Spacetime

We investigate the effects of spin on entanglement arising in Dirac field in an expanding spacetime characterized by the Robertson-Walker metric. We present a general approach that allows us to treat the case where only charge conservation is required, as well as the case where also angular momentum conservation is required. We find that in both situations entanglement originated from the vacuum and quantified by subsystem entropy behaves the same and does not qualitatively deviates from the spinless case. Differences only arise when particles and/or antiparticles are present in the input state.     

Induced-fit in the gas phase: conformational effects on the enantioselectivity of chiral tetra-amide macrocycles

The structure, stability, and reactivity of proton-bound diastereomeric [M x H x A]+ complexes between some amino acid derivatives (A) and several chiral tetra-amide macrocycles (M) have been investigated in the gas phase by ESI-FT-ICR and ESI-ITMS-CID mass spectrometry. The displacement of the A guest from the diastereomeric [M x H x A]+ complexes by reaction with the 2-aminobutane enantiomers (B) exhibits a distinct enantioselectivity with regards to the leaving amino acid A and, to a minor extent, to the amine reactant B. The emerging selectivity picture, discussed in the light of molecular mechanics calculations, provides compelling evidence that the most stable conformers of the selected chiral tetra-amide macrocycles M may acquire in the gas phase a different conformation by induced fit on complexation with some representative amino acid derivatives A. This leads to the coexistence in the gas phase of stable diastereomeric [M x H x A]+ eq-eq and ax-ax structures, in proportions depending on the configuration of A and M and characterized by different stability and reactivity toward the 2-aminobutane enantiomers. The enantioselectivity of the gas-phase A-to-B displacement in the diastereomeric [M x H x A]+ complexes essentially reflects the free energy gap between the homo- and heterochiral [M x H x A]+ complexes, except when the tetra-amidic host presents an additional macrocycle generated by a decamethylene chain. In this case, the measured enantioselectivity mostly reflects the stability difference between the relevant diastereomeric transition structures.     

Species with negative electron affinity and standard DFT methods. Finding the valence anions

Recently, we have shown that traditional bound-electron DFT models are reliable enough to reproduce negative electron affinities (EA) within a few meV, as long as the valence anion state is found, but they seem to fail in predicting the lowest EA when the ground anion state obtained is non-valence, which holds the extra electron in a diffuse orbital around the molecule; here we propose an alternative approach for finding the valence anion state, based on the stabilization exerted by a polar solvent; the methodology yields correct EA values (i.e. beyond the Koopman's theorem approximation) by gradually decreasing the dielectric constant of the medium.     

"Quasi flexible" automatic docking processing for studying stereoselective recognition mechanisms, part 2: Prediction of DeltaDeltaG of complexation and 1H-NMR NOE correlation

The purpose of this work is to apply the global molecular interaction evaluation ("Glob-MolInE") computational protocol to the study of two molecular complexes characterized by a chiral selector and a couple of enantiomeric selectands experimentally known to give large difference in the free energy of complexation much higher than the experimental error normally associated to the molecular mechanic calculations. We have considered the well known diastereomeric complexes between the selector (S)-N-(3,5-dinitrobenzoyl)-leucine-n-propylamide (S)-1 and the selectands (R) or (S)-N-(2-naphthyl)-alanine methyl ester 2, widely studied by enantioselective HPLC, NMR and X-ray. The experimental difference of free energy of complexation between [(S)-1*(R)-2] and [(S)-1*(S)-2] (-1.34 kcal/mol) was reproduced by the new computational protocol with an excellent confidence error. Detailed results about the conformational search, the "quasi-flexible" docking and the thermodynamic estimation are presented in this work. A remarkable correlation between the theoretical results and experimental data (NOE measurements, X-ray crystallographic structure of the [(S)-1*(S)-2] complex and the free energy of complexation) supports the validity of the computational approach and underline the importance of the conformational multiplicity in the definition of the macroscopic properties of the complex in solution.     

Electron ionization in LC-MS: recent developments and applications of the direct-EI LC-MS interface

The purpose of this article is to underline the possibility of efficiently using electron ionization (EI) in liquid chromatography (LC) and mass spectrometry (MS). From a historical perspective, EI accompanied the first attempts in LC-MS but, owing to several technical shortcomings, it was soon outshined by soft, atmospheric pressure ionization (API) techniques. Nowadays, two modern approaches, supersonic molecular beam LC-MS and direct-EI LC-MS, offer a valid alterative to API, and preserve the advantages of EI also in LC-MS applications. These advantages can be summarized in three crucial aspects: automated library identification; identification of unknown compounds, owing to EI extensive fragment information; inertness to coeluted matrix interferences owing to very unlikely ion–ion and ion–molecule interactions in the EI gas-phase environment. The direct-EI LC-MS interface is a simple and efficient solution able to produce high-quality, interpretable EI spectra from a wide range of low molecular weight molecules of different polarity. Because of the low operative flow rates, this interface relies on a nano-LC technology that helps in reducing the impact of the mobile phase on the gas-phase environment of EI. This review provides an extensive discussion on the role of EI in LC-MS interfacing, and presents in detail several performance aspects of the direct-EI LC-MS interface, especially in terms of response, mass-spectral quality, and matrix effects. In addition, several key applications are also reported.     

Chemoselective C-4 aerobic oxidation of catechin derivatives catalyzed by the Trametes villosa laccase/1-hydroxybenzotriazole system: synthetic and mechanistic aspects

Catechin derivatives were oxidized in air in the presence of the Trametes villosa laccase/1-hydroxybenzotriazole (HBT) system in buffered water/1,4-dioxane as reaction medium. The oxidation products, flavan-3,4-diols and the corresponding C-4 ketones, are bioactive compounds and useful intermediates for the hemisynthesis of proanthocyanidins, plant polyphenols which provide beneficial health properties for humans. Determinations of oxidation potentials excluded that catechin derivatives could be directly oxidized by laccase Cu(II), while it resulted in the H-abstraction from benzylic positions being promptly promoted by the enzyme in the presence of the mediator HBT, the parent species producing in situ the reactive intermediate benzotriazole-N-oxyl (BTNO) radical. A remarkable and unexpected result for the laccase/HBT oxidative system has been the chemoselective insertion of the oxygen atom into the C-4-H bond of catechin derivatives. Mechanistic aspects of the oxidation reaction have been investigated in detail for the first time in order to corroborate these results. Since the collected experimental findings could not alone provide information useful to clarify the origin of the observed chemoselectivity, these data were expressly supplemented with information derived by suitable molecular modeling investigations. The integrated evaluation of the dissociation energies of the C-H bonds calculated both by semiempirical and DFT methods and the differential activation energies of the process estimated by a molecular modeling approach suggested that the observed selective oxidation at the C-4 carbon has a kinetic origin.     

Laboratory Investigation of Variable-Density Flow and Solute Transport in Unsaturated–Saturated Porous Media

In many groundwater systems, fluid density and viscosity may vary in space and time as a function of changes in concentration and temperature of the fluid. When dense groundwater plumes interact with less dense ambient groundwater, these density variations can significantly affect flow and transport processes. Under certain conditions, gravitational instabilities in the form of lobe-shaped fingers can occur. This process is significant because it can lead to more rapid and spatially extensive solute transport. This paper presents new experiments carried out in a sand filled glass flow container under both fully saturated and variably-saturated conditions and focuses upon the processes that occur at the capillary fringe and below the water table, as affected by a dense contaminant plumes migration through the unsaturated zone. Source fluids stained with Rhodamine-WT were introduced at the upper boundary of the tank at a range of low and high densities. In addition to the fluid density gradients and porous medium permeability that determine the onset conditions for instabilities in fully saturated experiments, volumetric water content appears critical in the variably-saturated laboratory runs. Plume behaviour at the water table appears dependent upon the density of the fluid that accumulates there. For neutral and low density fluids, plumes accumulate at the water table and then spread laterally above it and the water table forms a barrier to further vertical flow as pore water velocities reduce with increasing water content. For medium and high density fluids, vertical movement continues as instabilities form at the capillary fringe and fingers begin to grow at the water table boundary and move downwards into the saturated zone. In these cases, lateral spreading of the plume is small. Despite these more qualitative observations, the exact nature of the relevant stability criteria for the onset and growth of instabilities in variably-saturated porous media presently remain unclear. All experimental results suggest, however, that the unsaturated zone and position of the water table must be considered in contaminant studies in order to predict the migration pathways, rates and ultimate fate of dense contaminant plumes. It is possible that the results of experiments presented in this paper could form a useful basis for the testing of variable-density (and variably-saturated) groundwater flow and solute transport numerical codes because they offer controlled physical laboratory analogs for comparison. They also provide a strong basis for the development of more rigorous mathematical formulations that are likely to be either developed or tested using numerical flow and solute transport simulators.     

A high-performance, flexible substrate for thin-film media

Advances in magnetic recording tape and flexible disk systems are limited to a large extent by the properties of the substrate, particularly for the case of evaporated or sputtered thin-film media. In this paper we report on the magnetic properties of thin-film media deposited onto a new high-performance polymeric film with improved tensile strength, which can withstand temperatures as high as 600°C without any adverse effects. Good magnetic properties were obtained by oblique incidence evaporation of cobalt films onto the heated substrates.