Amphiphilic Polymethacrylate‐ and Polystyrene‐Based Chemical Delivery Systems for Damascones

Amphiphilic polystyrene‐ and polymethacrylate‐based β‐acyloxy ketones were investigated as potential delivery systems for the controlled release of damascones by retro‐1,4‐addition in applications of functional perfumery. A series of random copolymers being composed of the hydrophobic damascone‐release unit and a second hydrophilic monomer were obtained by radical polymerization in organic solution by using 2,2′‐azobis[2‐methylpropanenitrile] (AIBN) as the radical source (Schemes 2 and 3). A first evaluation of the polymer conjugates in acidic or alkaline buffered aqueous solution, and in the presence of a surfactant, showed that polymethacrylates and polystyrenes having a carboxylic acid function as hydrophilic group are particularly interesting for the targeted applications (Table 2). The release of δ‐damascone ( 1 ) from polymers with poly(methacrylic acid) and poly(vinylbenzoic acid) comonomers in different stoichiometric ratios was thus followed over several days at pH 4, 7, and 9 by comparison of fluorescence probing, solvent extraction, and particle‐size measurements (Tables 3 and 4). In acidic media, the polymers were found to be stable, and almost no δ‐damascone ( 1 ) was released. In neutral or alkaline solution, where the carboxylic acid functions are deprotonated, the concentration of 1 increased over time. In the case of the polymethacrylates, the fluorescence probing experiments showed an increasing hydrophilicity of the polymer backbone with increasing fragrance release, whereas in the case of the polystyrene support, the hydrophilicity of the environment remained constant. These results suggest that the nature of the polymer backbone may have a stronger influence on the fragrance release than the ratio of hydrophilic and hydrophobic monomers in the polymer chain.     

Elementary Exponential Error Estimates for the Adiabatic Approximation

We present an elementary proof that the quantum adiabatic approximation is correct up to exponentially small errors for Hamiltonians that depend analytically on the time variable. Our proof uses optimal truncation of a straightforward asymptotic expansion. We estimate the terms of the expansion with standard Cauchy estimates.     

Neural activity associated with distinguishing concurrent auditory objects

The neural processes underlying concurrent sound segregation were examined by using event-related brain potentials. Participants were presented with complex sounds comprised of multiple harmonics, one of which could be mistuned so that it was no longer an integer multiple of the fundamental. In separate blocks of trials, short-, middle-, and long-duration sounds were presented and participants indicated whether they heard one sound (i.e., buzz) or two sounds (i.e., buzz plus another sound with a pure-tone quality). The auditory stimuli were also presented while participants watched a silent movie in order to evaluate the extent to which the mistuned harmonic could be automatically detected. The perception of the mistuned harmonic as a separate sound was associated with a biphasic negative-positive potential that peaked at about 150 and 350 ms after sound onset, respectively. Long duration sounds also elicited a sustained potential that was greater in amplitude when the mistuned harmonic was perceptually segregated from the complex sound. The early negative wave, referred to as the object-related negativity (ORN), was present during both active and passive listening, whereas the positive wave and the mistuning-related changes in sustained potentials were present only when participants attended to the stimuli. These results are consistent with a two-stage model of auditory scene analysis in which the acoustic wave is automatically decomposed into perceptual groups that can be identified by higher executive functions. The ORN and the positive waves were little affected by sound duration, indicating that concurrent sound segregation depends on transient neural responses elicited by the discrepancy between the mistuned harmonic and the harmonic frequency expected based on the fundamental frequency of the incoming stimulus.     

Rotational Analysis of the ΔvSiH=3-6 Stretching Vibrational Overtones of HSiD3

The nν₁ SiH stretching overtone transitions of trideuterosilane, HSiD₃, have been recorded by Fourier transform spectroscopy (n=3 and 4) and by intracavity laser absorption spectroscopy (n=5 and 6). The unusually weak 3ν₁ band is affected by considerable intensity and energy perturbations. The 4ν₁ band is also strongly perturbed but the interaction with the dark states is more limited and part of the rotational structure of the v₁=4 upper state could be satisfactorily modeled. Less pronounced perturbations affect the v₁=5 level, newly detected by ICLAS. Its rotational structure is locally perturbed by anharmonic coupling with an unidentified vibrational dark state. The global modeling of the interacting dyad allowed the determination of the perturber parameters and the assignment of extra lines due to an intensity transfer from the v₁=5 bright state to the dark state. In agreement with a previous ICLAS study, the 6ν₁ band near 12 113 cm⁻¹ was found free of perturbation. About six hundred line positions could be reproduced with an rms of 4.6×10⁻³ cm⁻¹, leading to a significantly improved set of rovibrational parameters. The striking evolution of the rotational structure, which exhibits fewer and fewer perturbations when the SiH excitation increases, is discussed.     

On Quantum Phase Transition. II. The Falicov–Kimball Model

The Falicov–Kimball (FK) model⁽¹⁾ involves two types of interacting particles: first the itinerant spinless electrons are quantum particles, secondly the static ions are classical particles. It is striking to see that, despite the simplicity of its hamiltonian, the phase diagram of the FK model is highly sophisticated, moreover it remains in great part conjectural. An antiferromagnetic phase transition was proven for the FK model on a square lattice in the seminal paper of T. Kennedy and E. Lieb.⁽²⁾ This result was extended by Lebowitz and Macris⁽³⁾ to small magnetic field. Then the same result was obtained by using a new method.⁽⁴⁾ The main results of this paper concerns the two dimensional FK model on a square lattice, for which we apply the general results contained in ref. 5. First there exists an effective hamiltonian which is a long range many body Ising model, and which governs the behaviour of the ions. Secondly we compute explicitly the truncated effective hamiltonian up to the fourth order w.r.t. a small parameter (the inverse of the on site energy). Finally we use the classical Pirogov–Sinai theory, to get the hierarchy of the phase diagrams up to the fourth order. More precisely, we show that, when the chemical potential varies, the FK model exhibits, at low temperature, a sequence of phase transitions: first between phases of period two, then of period three, then of period four, and finally of period five. In each case the completeness of the phase diagram is proved. This paper supports the conjecture that the phase diagram of the FK model contains periodic phases outside of a Cantor set.     

Macrotricyclic quaternary tetraammonium receptors: halide anion recognition and interfacial activity at an aqueous interface. A molecular dynamics investigation

We report a molecular dynamics study of the halide inclusion complexes X(-) subset L(4+) of a macrotricyclic tetrahedral receptor L(4+) built from four quaternary ammonium sites connected by six (CH(2))(n) chains. The hydrophilic/hydrophobic character of the complexes is investigated at a water/chloroform interface, represented explicitly and, despite their +3 charge and "spherical" shape, they are found to display amphiphilic behavior and to concentrate at the interface. The more lipophilic N-substituted CH(2)phi derivative, as well as less charged models are more surface active than the N-Me substituted host. In relation with the Hofmeister series, I(-) exo neutralizing counterions are compared with Cl(-) anions and are found to sit closer to the interface, which becomes more neutral. The "macrocyclic interfacial effect" is investigated by a comparison of L(4+) complexes with their acyclic counterparts. Finally, we address the question of anion binding selectivity by L(4+) and its L(1) (4+) and L(2) (4+) topological isomers. F(-) is too small for these three hosts, while I(-) is too big. According to free energy perturbation calculations, Cl(-) is preferred to Br(-), but somewhat more by L(1) (4+) than by L(4+).     

Dynamic behavior in diplatinum metalloreceptors

Diplatinum metalloreceptors anti-4a and anti-4b exhibit dynamic behavior in solution that is modified by anion binding. An X-ray crystal structure determination of anti-4a supports its proposed solution structure.     

Characterization of multimetallic grid-type complexes by electrospray mass spectrometry

The self-assembly of the terdentate ligands 1a-h, based on terpyridine-like binding sites, with octahedrally coordinated metal ions, such as Fe(II), Co(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II), leads to the formation of the supramolecular grid-type complexes 2a-c(M(II)), 3d-g(M(II)) and 4h(M(II)). The structures and compositions of these coordination complexes in solution were deduced from electrospray mass spectrometry (ESMS) measurements. The results agree with the data available from x-ray radiocrystallography in the solid state and/or NMR spectroscopy in solution. ESMS may be applied in cases where other methods are difficult to use or inconclusive. This study stresses the power of ESMS in supramolecular chemistry.     

On Quantum Phase Transition. I. Spinless Electrons Strongly Correlated with Ions

We study a large class F of models of the quantum statistical mechanics dealing with two types of particles. First the spinless electrons are quantum particles obeying to the Fermi statistics, they can hop. Secondly the ions which cannot move, are classical particles. The Falicov–Kimball (FK) model⁽¹⁾ is a well known model belonging to F, for which the existence of an antiferomagnetic phase transition was proven in the seminal paper of Kennedy and Lieb.⁽²⁾ This result was extended by Lebowitz and Macris.⁽³⁾ A new approach to this problem based on quantum selection of the ground states was proposed in ref. 4. In this paper we extend this approach to show that, under the strong insulating condition, any hamiltonian of the class F admits, at every temperature, an effective hamiltonian, which governs the behaviour of the ions interacting through forces mediated by the electrons. The effective hamiltonians are long range many body Ising hamiltonians, which can be computed by a cluster expansion expressed in term of the quantum fluctuations. Our main result is that we can apply the powerfull results of the classical statistical mechanics to our quantum models. In particular we can use the classical Pirogov–Sinai theory to establish a hierarchy of phase diagrams, we can also study of the behaviour of the quantum inter- faces,⁽²⁹⁾ and so on...     

Self-sum- and -difference-frequency mixing in GdAl(3)(BO(3))(4):Nd(3+) for generation of tunable ultraviolet and infrared radiation

We exploited Nd(3+) laser emission at 1061.9 nm ((4)F(3/2)?(4)I(11/2) channel) in a self-chi((2)) active GdAl(3)(BO(3))(4):Nd(3+) laser crystal. UV radiation was obtained from a 1.8% yield from self-sum-frequency mixing: 1/pump + 1/1061.9 = 1/UV, during pumping in the Nd(3+) (4)G(5/2)-(2)G(7/2) levels near 588 nm. The UV tunability had a range of 378-382 nm. We have demonstrated, for the first time to our knowledge, generation of coherent IR radiation from a self-difference-frequency mixing laser: 1/pump - 1/1061.9 = 1/IR. We got a 0.5% yield and tunability in the 1305-1365-nm range.