Polar substituent effects in the bicyclo[1.1.1]pentane ring system: acidities of 3-substituted bicyclo[1.1.1]pentane-1-carboxylic acids

Experimental gas-phase acidities are reported for a series of 3-substituted (X) bicyclo [1.1.1]pent-1-yl carboxylic acids (1, Y = COOH). A comparison with available calculated data (MP2/6-311++G**// B3LYP/6-311+G**) reveals good agreement. The relative substituent effects are shown to be adequately described by a much lower level of theory (B3LYP/6-31+G*). Various correlations are presented which clearly point to polar field effects as being the origin of the relative acidities.     

Hindered inversion of chiral ion-dipole pairs.

O-Protonated S-(-)-1-phenyl-1-methoxyethane (IS) has been generated in the gas phase by CH3(2)Cl+ methylation of S-(-)-1-phenylethanol (1S). Detailed information on the reorganization dynamics of the intimate ion-dipole pair (IIS), arising from IS by C-O bond dissociation, is inferred from the kinetic study of the intramolecular inversion of configuration of IS vs its dissociation to alpha-methylbenzyl cation (III) and CH(3)OH. The behavior of IIS in the gas phase is compared to that observed in aqueous solutions, where the loss of optical activity of IS is prevented by exchange of the leaving CH3OH with the solvent shell. Hindered inversion of IS in solution is attributed to the operation of attractive interactions between the moving CH3OH moiety and the solvent cage which inhibit internal return in the intimate ion-dipole pair IIS. Similar interactions do not operate in the solvolysis of 18O-labeled 1S in aqueous acids, whose loss of optical activity efficiently competes with exchange of the leaving H2(18)O with the solvent shell.     

Troposelective substitutions in microsolvated systems.

The mechanism and the stereochemistry of the intracomplex "solvolysis" of the proton-bound complexes I(X)() between CH(3)(18)OH and (R)-(+)-1-aryl-ethanol (1(R)()(X)(); aryl = phenyl (X = H); pentafluorophenyl (X = F)) have been investigated in the gas phase in the 25-100 degrees C temperature range. The results point to intracomplex "solvolysis" as proceeding through the intermediacy of the relevant benzyl cation III(X)() (a pure S(N)1 mechanism). "Solvolysis" of I(H)() leads to complete racemization at T > 50 degrees C, whereas at T < 50 degrees C the reaction displays a preferential retention of configuration. Predominant retention of configuration is also observed in the intracomplex "solvolysis" of I(F)(). This picture is rationalized in terms of different intracomplex interactions between the benzylic ion III(X)() and the nucleophile/leaving group pair, which govern the timing of their reorientation within the electrostatic complex. The obtained gas-phase picture is discussed in the light of related gas-phase and solution data. It is concluded that the solvolytic reactions are mostly governed by the lifetime and the dynamics of the species involved and, if occurring in solution, by the nature of the solvent cage. Their rigid subdivision into the S(N)1 and S(N)2 mechanistic categories appears inadequate, and the use of their stereochemistry as a mechanistic probe can be highly misleading.     

Comparison of solution-blending and melt-intercalation for the preparation of poly(ethylene-co-acrylic acid)/organoclay nanocomposites

Ethylene-acrylic acid copolymers (EAAs) and commercial montmorillonite clays organically modified with dimethyldihydrogenatedtallowammonium ions (Cloisite^® 15A and 20A) were used for the synthesis of nanocomposites by melt-compounding, static melting of polymer/clay mixtures and solution-intercalation in order to compare the effectiveness of these procedures and to shed light on the thermodynamics and the kinetics of the intercalation process. The preparation from solution was made by the use of several solvents, such as toluene, xylene, chloroform, etc., which were then removed from the hybrids by precipitation in different non-solvents or by evaporation. Particular attention was paid to the effect of the thermal treatments which are often used when processing the composites prepared from solution. X-ray diffraction (XRD) of the solution-blended composites showed that no intercalation of the EAAs inside the clay galleries can be achieved if solvent removal is made by precipitation in non-solvents or by room-temperature evaporation. On the contrary, intercalation was found to occur very rapidly (in less than 1 min) when both the hybrids prepared from solution and the mechanical blends of powdered components were melted in the absence of shear. Polymer intercalation was also found to occur, though with a lower rate, upon annealing the powder mixtures at temperatures lower than the EAA melting point. Microscopic observations made by polarized optical microscopy, scanning electron microscopy and transmission electron microscopy showed that the clay particles dispersion is appreciably lower for the composites prepared from solution, compared to those produced in the melt under shear flow conditions. The hybrids obtained by static melting of powder mixtures, on the other side, were expectedly found to comprise micron sized clay agglomerates, although intercalation was demonstrated also for these materials by XRD. The structure of the intercalated silicate layers stacks, characterized by an interlayer spacing of 4.0 nm, was shown to be independent of the preparation procedure and to correspond to thermodynamic equilibrium.     

Facial selectivity of the (R)-1,3-dimethyl-1-cyclohexyl cation in the gas phase

The model reaction between the (R)-1,3-dimethyl-1-cyclohexyl cation (I) and methanol has been investigated under gas-phase radiolytic conditions (750 Torr; 25-120 degrees C) with the aim of evaluating the intrinsic factors that govern the facial selectivity of biased carbocations. The peculiarity of the experimental approach allows the formation of different CH(3) (18)OH.I ionic adducts. Subsequent conversion of these adducts to give the corresponding E/Z covalent products follows different reaction coordinates, which are characterized by their own activation parameters. On the grounds of density functional theory (DFT) results, several [CH(3)OH.I] structures have been located on the relevant potential-energy surface (PES). The experimental results point to a gas-phase facial selectivity, which is mainly governed by entropic factors that arise as a result of the occurrence of different noncovalent ion-molecule "facial adducts" (FA). The formation of FAs may also play an important role in both the reaction dynamics and the positional selectivity. The present results cannot be interpreted by any of the models based on solution-phase experiments.     

On the Origin of Primitive Cells: From Nutrient Intake to Elongation of Encapsulated Nucleotides

Recent major discoveries in membrane biophysics hold the key to a modern understanding of the origin of life on Earth. Membrane bilayer vesicles have been shown to provide a multifaceted microenvironment in which protometabolic reactions could have developed. Cell‐membrane‐like aggregates of amphiphilic molecules capable of retaining encapsulated oligonucleotides have been successfully created in the laboratory. Sophisticated laboratory studies on the origin of life now show that elongation of the DNA primer takes place inside fatty acid vesicles when activated nucleotide nutrients are added to the external medium. These studies demonstrate that cell‐like vesicles can be sufficiently permeable to allow for the intake of charged molecules such as activated nucleotides, which can then take part in copying templates in the protocell interior. In this Review we summarize recent experiments in this area and describe a possible scenario for the origin of primitive cells, with an emphasis on the elongation of encapsulated nucleotides.     

Unexpected Behavior of Diastereomeric Ions in the GasPhase: A Stimulus for Pondering on ee Measurements by ESI-MS

The most common protocols for the quantitative determination of the enantiomeric excess (ee) of raw mixtures by ESI-MS reveal inadequate in cases where the distribution of diastereomeric derivatives diverges from the ee of original solutions. This phenomenon is attributable to a matrix effect, i.e., to the stereospecific formation of high order noncovalent adducts in the ESI droplets, which alters the actual availability of the diastereomeric species under MS analysis. In this frame, the assumption of classic protocols that the ionization correction factor q is independent on the composition of the mixture submitted to analysis is questionable. An alternative methodology is presented in this paper, which is aimed at circumventing the problem by excluding any chemical derivatization of the original raw mixture. It is based on the measurement of the actual distribution of ESI-formed proton-bound diastereomeric complexes from the enantiomeric mixture through a careful analysis of their reaction kinetics with a suitable reactant.      

In situ thermal treatment of UV-oxidized diamond hydrogenated surface

Surface properties of polycrystalline hydrogenated diamond produced by chemical vapour deposition upon oxidation under UV irradiation are studied. The diamond surfaces were cleaned in vacuum by thermal treatment. They were characterized estimating the electron affinity of the virgin surface by UV photoelectron spectroscopy and controlling the surface composition by X-ray photoelectron spectroscopy. The cleaned surfaces were then exposed to pure oxygen and UV radiation (deuterium lamp). Ozone induced surface oxidation was verified by XPS estimating the oxygen atomic concentration and the presence of specific chemical bonds. Surface oxidation was also verified analyzing the change in the diamond electron affinity. Oxygen was then removed in situ by a series of thermal treatments at increasing temperature. Already at ～300 °C a remarkable reduction of the oxygen concentration occurs which persists increasing the annealing temperature. Contemporary, a progressive recovery of the initial electron affinity is also obtained. These effects are observed up to 970 °C, a temperature at which the electron affinity assumes a negative value. Specific chemical reactions are hypothesized to describe the oxidation process and to explain the electronic behaviour of the diamond surface.