Selectivity and Mechanisms Driven by Reaction Dynamics: The Case of the Gas-Phase OH-+CH3ONO2 Reaction

Well-established statistical approaches such as transition-state theory based on high-level calculated potential energy profiles are unable to account for the selectivity observed in the gas-phase OH- + CH3ONO2 reaction. This reaction can undergo bimolecular nucleophilic displacement at either the carbon center (S(N)2@C) or the nitrogen center (S(N)2@N) as well as a proton abstraction followed by dissociation (E(CO)2) pathway. Direct dynamics simulations yield an S(N)2:E(CO)2 product ratio in close agreement with experiment and show that the lack of reactivity at the nitrogen atom is due to the highly negative electrostatic potential generated by the oxygen atoms in the ONO2 group that scatters the incoming OH-. In addition to these dynamical effects, the nonstatistical behavior of these reactions is attributed to the absence of equilibrated reactant complexes and to the large number of recrossings, which might be present in several ion-molecule gas-phase reactions.

Gas-phase reactivity of protonated 2-oxazoline derivatives: mass spectrometry and computational studies

RATIONALE: Oxazolines have attracted the attention of researchers worldwide due to their versatility as carboxylic acid protecting groups, chiral auxiliaries, and ligands for asymmetric catalysis. Electrospray ionization tandem mass spectrometric (ESI-MS/MS) analysis of five 2-oxazoline derivatives has been conducted, in order to understand the influence of the side chain on the gas-phase dissociation of these protonated compounds under collision-induced dissociation (CID) conditions. METHODS: Mass spectrometric analyses were conducted in a quadrupole time-of-flight (Q-TOF) spectrometer fitted with electrospray ionization source. Protonation sites have been proposed on the basis of the gas-phase basicity, proton affinity, atomic charges, and a molecular electrostatic potential map obtained on the basis of the quantum chemistry calculations at the B3LYP/6-31 + G(d, p) and G2(MP2) levels. RESULTS: Analysis of the atomic charges, gas-phase basicity and proton affinities values indicates that the nitrogen atom is a possible proton acceptor site. On the basis of these results, two main fragmentation processes have been suggested: one taking place via neutral elimination of the oxazoline moiety (99 u) and another occurring by sequential elimination of neutral fragments with 72 u and 27 u. These processes should lead to formation of R+. CONCLUSIONS: The ESI-MS/MS experiments have shown that the side chain could affect the dissociation mechanism of protonated 2-oxazoline derivatives. For the compound that exhibits a hydroxyl at the lateral chain, water loss has been suggested to happen through an E2-type elimination, in an exothermic step. Copyright (C) 2012 John Wiley & Sons, Ltd.

Rounding of a first-order quantum phase transition to a strong-coupling critical point

We investigate the effects of quenched disorder on first-order quantum phase transitions on the example of the N-color quantum Ashkin-Teller model. By means of a strong-disorder renormalization group, we demonstrate that quenched disorder rounds the first-order quantum phase transition to a continuous one for both weak and strong coupling between the colors. In the strong-coupling case, we find a distinct type of infinite-randomness critical point characterized by additional internal degrees of freedom. We investigate its critical properties in detail and find stronger thermodynamic singularities than in the random transverse field Ising chain. We also discuss the implications for higher spatial dimensions as well as unusual aspects of our renormalization-group scheme. DOI: 10.1103/PhysRevB.86.214204

Stripe-tetragonal phase transition in the two-dimensional Ising model with dipole interactions: Partition function zeros approach

We have performed multicanonical simulations to study the critical behavior of the two-dimensional Ising model with dipole interactions. This study concerns the thermodynamic phase transitions in the range of the interaction delta where the phase characterized by striped configurations of width h = 1 is observed. Controversial results obtained from local update algorithms have been reported for this region, including the claimed existence of a second-order phase transition line that becomes first order above a tricritical point located somewhere between delta = 0.85 and 1. Our analysis relies on the complex partition function zeros obtained with high statistics from multicanonical simulations. Finite size scaling relations for the leading partition function zeros yield critical exponents. that are clearly consistent with a single second-order phase transition line, thus excluding such a tricritical point in that region of the phase diagram. This conclusion is further supported by analysis of the specific heat and susceptibility of the orientational order parameter.

Light scattering on the structural characterization of DMPG vesicles along the bilayer anomalous phase transition

Highly charged vesicles of the saturated anionic lipid dimyristoyl phosphatidylglycerol (DMPG) in low ionic strength medium exhibit a very peculiar thermo-structural behavior. Along a wide gel-fluid transition region, DMPG dispersions display several anomalous characteristics, like low turbidity, high electrical conductivity and viscosity. Here, static and dynamic light scattering (SLS and DLS) were used to characterize DMPG vesicles at different temperatures. Similar experiments were performed with the largely studied zwitterionic lipid dimyristoyl phosphatidylcholine (DMPC). SLS and DLS data yielded similar dimensions for DMPC vesicles at all studied temperatures. However, for DMPG, along the gel-fluid transition region, SLS indicated a threefold increase in the vesicle radius of gyration, whereas the hydrodynamic radius, as obtained from DLS, increased 30% only. Despite the anomalous increase in the radius of gyration, DMPG lipid vesicles maintain isotropy, since no light depolarization was detected. Hence, SLS data are interpreted regarding the presence of isotropic vesicles within the DMPG anomalous transition, but highly perforated vesicles, with large holes. DLS/SLS discrepancy along the DMPG transition region is discussed in terms of the interpretation of the Einstein-Stokes relation for porous vesicles. Therefore, SLS data are shown to be much more appropriate for measuring porous vesicle dimensions than the vesicle diffusion coefficient. The underlying nanoscopic process which leads to the opening of pores in charged DMPG bilayer is very intriguing and deserves further investigation. One could envisage biotechnological applications, with vesicles being produced to enlarge and perforate in a chosen temperature and/or pH value. (C) 2012 Elsevier Ireland Ltd. All rights reserved.

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.

Sequential Methyl-Fluorine Exchange Reactions of Siloxide Ions in the Gas Phase

Air Force Office of Scientific Research (AFOSR)

Analysis of phase transition and dehydration processes of nevirapine

Solid-state characterization of crystalline drugs is an important pre-formulation step for the development and design of solid dosage forms, such as pellets and tablets. In this study, phase transition and dehydration processes of nevirapine have been studied by differential scanning calorimetry and thermogravimetry differential thermal analysis to overcome the problems of drug formulation, namely poor solubility and poor content uniformity. Phase solubility studies elucidated the mechanism of enhanced nevirapine solubility.

Phase Transition for the Ising Model on the Critical Lorentzian Triangulation

The ferromagnetic Ising model without external field on an infinite Lorentzian triangulation sampled from the uniform distribution is considered. We prove uniqueness of the Gibbs measure in the high temperature region and coexistence of at least two Gibbs measures at low temperature. The proofs are based on the disagreement percolation method and on a variant of the Peierls contour method. The critical temperature is shown to be constant a.s.

Gas-phase reactivity of 2-hydroxy-1,4-naphthoquinones: a computational and mass spectrometry study of lapachol congeners

In order to understand the influence of alkyl side chains on the gas-phase reactivity of 1,4-naphthoquinone derivatives, some 2-hydroxy-1,4-naphthoquinone derivatives have been prepared and studied by electrospray ionization tandem mass spectrometry in combination with computational quantum chemistry calculations. Protonation and deprotonation sites were suggested on the basis of gas-phase basicity, proton affinity, gas-phase acidity (?Gacid), atomic charges and frontier orbital analyses. The nature of the intramolecular interaction as well as of the hydrogen bond in the systems was investigated by the atoms-in-molecules theory and the natural bond orbital analysis. The results were compared with data published for lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone). For the protonated molecules, water elimination was verified to occur at lower proportion when compared with side chain elimination, as evidenced in earlier studies on lapachol. The side chain at position C(3) was found to play important roles in the fragmentation mechanisms of these compounds. Copyright (c) 2012 John Wiley & Sons, Ltd.

The β to α phase transition of tantalum coatings deposited by modulated pulsed power magnetron sputtering

Tantalum coatings are of particular interest today as promising candidates to replace potentially hazardous electrodeposited chromium coatings for tribological and corrosion resistant applications, such as the internal lining on large-caliber gun barrels. Tantalum coatings have two crystalline phases, α-Ta (body-centered-cubic) and β-Ta (metastable tetragonal) that exhibit relatively different properties. Alpha-Ta is typically preferred for wear and corrosion resistant applications and unfortunately, is very difficult to deposit without the assistance of substrate heating or post-annealing treatments. Furthermore, there is no general consensus on the mechanism which causes α or β to form or if there is a phase transition or transformation from β → α during coating deposition. In this study, modulated pulsed power (MPP) magnetron sputtering was used to deposit tantalum coatings with thicknesses between 2 and 20 μm without external substrate heating. The MPP Ta coatings showed good adhesion and low residual stress. This study shows there is an abrupt β → α phase transition when the coating is 5–7 μm thick and not a total phase transformation. Thermocouple measurements reveal substrate temperature increases as a function of deposition time until reaching a saturation temperature of ~ 388 °C. The importance of substrate temperature evolution on the β → α phase transition is also explained.

Oligonucleotide Adsorption Affects Phase Transition but Not Interdigitation of diC14-Amidine Bilayers

Oligonucleotides have been extensively used in basic research of gene expression and function, vaccine design, and allergy and cancer therapy. Several oligonucleotide-based formulations have reached the clinical trial phase and one is already on the market. All these applications, however, are dependent on suitable carriers that protect oligonucleotides against degradation and improve their capture by target cells. The cationic lipid diC14-amidine efficiently delivers nucleic acids to mammalian cells. It was recently shown that diC14-amidine bilayers present an interdigitated phase which strongly correlates with a potent fusogenic activity at low temperatures. Interdigitated phases correspond to very ordered gel phases where the two bilayer leaflets are merged; they usually result from perturbations at the interfacial region such as modifications of the polar headgroup area or dehydration of the bilayer. Interdigitation has been described for asymmetric lipids or mixed-chain lipids of different chain lengths and for lipids with large effective headgroup sizes. It has also been described for symmetric lipids under pressure modifications or in the presence of alcohol, glycerol, acetonitrile, polymyxin B, or ions like thiocyanate. Surprisingly, the role of polyelectrolytes on membrane interdigitation has been only poorly investigated. In the present work, we use dynamic light scattering (DLS), differential scanning calorimetry (DSC), and electron spin resonance (ESR) to explore the effect of a small single-stranded oligonucleotide (ODN) polyelectrolyte on the structure and colloid stability of interdigitated diC14-amidine membranes.

Quantum oscillations of spin polarization in a GaAs/AlGaAs double quantum well

5 We employ the circular-polarization-resolved magnetophotoluminescence technique to probe the spin character of electron and hole states in a GaAs/AlGaAs strongly coupled double-quantum-well system. The photoluminescence (PL) intensities of the lines associated with symmetric and antisymmetric electron states present clear out-of-phase oscillations between integer values of the filling factor. and are caused by magnetic-field-induced changes in the population of occupied Landau levels near to the Fermi level of the system. Moreover, the degree of circular polarization of these emissions also exhibits the oscillatory behavior with increasing magnetic field. Both quantum oscillations observed in the PL intensities and in the degree of polarizations may be understood in terms of a simple single-particle approach model. The k . p method was used to calculate the photoluminescence peak energies and the degree of circular polarizations in the double-quantum-well structure as a function of the magnetic field. These calculations prove that the character of valence band states plays an important role in the determination of the degree of circular polarization and, thus, resulting in a magnetic-field-induced change of the polarization sign.

Quantum critical scaling at a Bose-glass/superfluid transition: Theory and experiment for a model quantum magnet

In this paper we investigate the quantum phase transition from magnetic Bose Glass to magnetic Bose-Einstein condensation induced by amagnetic field in NiCl2 center dot 4SC(NH2)(2) (dichloro-tetrakis-thiourea-nickel, or DTN), doped with Br (Br-DTN) or site diluted. Quantum Monte Carlo simulations for the quantum phase transition of the model Hamiltonian for Br-DTN, as well as for site-diluted DTN, are consistent with conventional scaling at the quantum critical point and with a critical exponent z verifying the prediction z = d; moreover the correlation length exponent is found to be nu = 0.75(10), and the order parameter exponent to be beta = 0.95(10). We investigate the low-temperature thermodynamics at the quantum critical field of Br-DTN both numerically and experimentally, and extract the power-law behavior of the magnetization and of the specific heat. Our results for the exponents of the power laws, as well as previous results for the scaling of the critical temperature to magnetic ordering with the applied field, are incompatible with the conventional crossover-scaling Ansatz proposed by Fisher et al. [Phys. Rev. B 40, 546 (1989)]. However they can all be reconciled within a phenomenological Ansatz in the presence of a dangerously irrelevant operator.

Percolation transition in quantum Ising and rotor models with sub-Ohmic dissipation

We investigate the influence of sub-Ohmic dissipation on randomly diluted quantum Ising and rotor models. The dissipation causes the quantum dynamics of sufficiently large percolation clusters to freeze completely. As a result, the zero-temperature quantum phase transition across the lattice percolation threshold separates an unusual super-paramagnetic cluster phase from an inhomogeneous ferromagnetic phase. We determine the low-temperature thermodynamic behavior in both phases, which is dominated by large frozen and slowly fluctuating percolation clusters. We relate our results to the smeared transition scenario for disordered quantum phase transitions, and we compare the cases of sub-Ohmic, Ohmic, and super-Ohmic dissipation.