Asymptotic Dynamics in Populations Structured by Sensitivity to Global Warming and Habitat Shrinking

How to recast effects of habitat shrinking and global warming on evolutionary dynamics into continuous mutation/selection models? Bearing this question in mind, we consider differential equations for structured populations, which include mutations, proliferation and competition for resources. Since mutations are assumed to be small, a parameter ε is introduced to model the average size of phenotypic changes. A well-posedness result is proposed and the asymptotic behavior of the density of individuals is studied in the limit ε→0. In particular, we prove the weak convergence of the density to a sum of Dirac masses and characterize the related concentration points. Moreover, we provide numerical simulations illustrating the theorems and showing an interesting sample of solutions depending on parameters and initial data.     

Synthetic Applications of Stereodefined 2-Substituted 1-Silyl-1-stannylethenes: A New Synthesis of 5-Ethenyl-5′-(1-propynyl)-2,2′-bithiophene,a Naturally-Occurring Phototoxin)

(E)-2-(5-Trimenthylstannyl-2-thienyl)ethenyldimethylphenylsilane. (E)-8, which can be stereospecifically prepared from (Z)-1-dimethylphenylsilyl-2-(2-thienyl)-1-trimethylstannyl-ethene, (Z)-6, or from (E)-2-(2-thienyl)ethenyldimethylphenylsilane, (E)-9, serves as an equivalent to the 2-ethenylthiophene d ¹', d ⁵-synthon, 20, in an efficient two-step synthesis of 5-ethenyl-5′-(1-propynyl)-2,2′-bithiophene, 10, a naturally-occurring phototoxin. In the first step of this synthesis compound (E)-8 undergoes a palladium-catalyzed cross-coupling reaction with 2-iodo-5-(1-propynyl)thiophene, 16, and in th second step the so obtained cross-coupling product, (E)-17, undergoes a protodesilylation reaction.     

Photophysical Properties and Conformational Effects on the Circular Dichroism of an Azobenzene–Cyclodextrin [1]Rotaxane and Its Molecular Components

The photophysical properties of a multicomponent [1]rotaxane bearing a β‐cyclodextrin ring covalently connected to an axle comprising an azobenzene photoisomerisable moiety and a naphthalimide‐type fluorescent stopper are investigated by a combined experimental and computational study. The absorption and fluorescence spectra, and particularly the induced circular dichroism (ICD) signal, are determined. The latter shows a sign relation that cannot be rationalised in terms of the simple general rules commonly employed to analyse the ICD spectra of achiral guests encircled by chiral hosts. To assist the interpretation of experimental results, DFT and time‐dependent (TD) DFT calculations are performed to explore the availability of low‐energy conformations and to model their spectroscopic response. Molecular dynamics simulations performed in water show the interconversion of a number of conformers, the contribution of which to the ICD signal is in agreement with the observation.     

Optimal control technique for many-body quantum dynamics

We present an efficient strategy for controlling a vast range of nonintegrable quantum many-body one-dimensional systems that can be merged with state-of-the-art tensor network simulation methods such as the density matrix renormalization group. To demonstrate its potential, we employ it to solve a major issue in current optical-lattice physics with ultracold atoms: we show how to reduce by about 2 orders of magnitude the time needed to bring a superfluid gas into a Mott insulator state, while suppressing defects by more than 1 order of magnitude as compared to current experiments [T. St?ferle et al., Phys. Rev. Lett. 92, 130403 (2004)]. Finally, we show that the optimal pulse is robust against atom number fluctuations.     

Hydrogen-Bond Structure and Low-Frequency Dynamics of Electrolyte Solutions: Hydration Numbers from ab Initio Water Reorientation Dynamics and Dielectric Relaxation Spectroscopy

We present an atomistic simulation scheme for the determination of the hydration number (h) of aqueous electrolyte solutions based on the calculation of the water dipole reorientation dynamics. In this methodology, the time evolution of an aqueous electrolyte solution generated from ab initio molecular dynamics simulations is used to compute the reorientation time of different water subpopulations. The value of h is determined by considering whether the reorientation time of the water subpopulations is retarded with respect to bulk-like behavior. The application of this computational protocol to magnesium chloride (MgCl₂) solutions at different concentrations (0.6–2.8 mol kg⁻¹) gives h values in excellent agreement with experimental hydration numbers obtained using GHz-to-THz dielectric relaxation spectroscopy. This methodology is attractive because it is based on a well-defined criterion for the definition of hydration number and provides a link with the molecular-level processes responsible for affecting bulk solution behavior. Analysis of the ab initio molecular dynamics trajectories using radial distribution functions, hydrogen bonding statistics, vibrational density of states, water-water hydrogen bonding lifetimes, and water dipole reorientation reveals that MgCl₂ has a considerable influence on the hydrogen bond network compared with bulk water. These effects have been assigned to the specific strong Mg-water interaction rather than the Cl-water interaction.     

A new sustainable protocol for the synthesis of nitroaldol derivatives via Henry reaction under solvent-free conditions

A new protocol for the Henry addition of nitroalkanes to aryl- and alkyl-aldehydes promoted by PS-BEMP under solvent-free conditions (SolFC) is presented. The corresponding nitroaldol products were obtained in good yields and short times; furthermore minimization of the reaction waste was achieved by reducing the use of organic solvents. Extension of the protocol was obtained by setting up the tandem Michael-Henry reaction of α,β-unsaturated aldehydes and nitroalkane to yield the corresponding dinitro derivatives.     

Solid‐State NMR of PEGylated Proteins

PEGylated proteins are widely used in biomedicine but, in spite of their importance, no atomic‐level information is available since they are generally resistant to structural characterization approaches. PEGylated proteins are shown here to yield highly resolved solid‐state NMR spectra, which allows assessment of the structural integrity of proteins when PEGylated for therapeutic or diagnostic use.     

Monatomic gas as a singular limit of polyatomic gas in molecular extended thermodynamics with many moments

The difference in the theoretical structure between monatomic and polyatomic gases in highly nonequilibrium states is discussed from the viewpoint of molecular extended thermodynamics (MET) of rarefied gases, which is free from the local equilibrium assumption. The MET theories of these two types of gases are based on the moment balance equations with different hierarchy structures due to whether the internal degrees of freedom of a molecule are incorporated in their distribution functions or not. In particular, the number of balance equations in the MET theory of polyatomic gases is greater than the number in the corresponding theory of monatomic gases. The closure procedure for the system of balance equations of polyatomic gases obtained in a recent paper (Arima et al., 2014) is adopted. We prove that the solutions for polyatomic gases converge, in the limit where the degrees of freedom of a molecule D$D$ tend to 3, to the ones for monatomic gases provided that we impose appropriate initial conditions compatible with monatomic gases. Thus a MET theory of rarefied monatomic gases can be identified as a singular limit of the corresponding MET theory of rarefied polyatomic gases. As illustrative examples, the asymptotic behaviors when D→3$D\to 3$ in the dispersion relation of ultrasonic waves and in the shock wave structure are shown.     

Profiling of N-acyl-homoserine lactones by liquid chromatography coupled with electrospray ionization and a hybrid quadrupole linear ion-trap and Fourier-transform ion-cyclotron-resonance mass spectrometry (LC-ESI-LTQ-FTICR-MS)

A method for the comprehensive profiling of the N-acyl-homoserine lactone (AHL) family of bacterial quorum-sensing molecules is presented using liquid chromatography (LC) coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier-transform ion-cyclotron-resonance mass spectrometer (FTICR). We demonstrate an increase in signal intensity in MS with electrospray ionization (ESI) of the protonated molecules, [M + H](+), by using acetonitrile (ACN) instead of methanol (MeOH) as the organic solvent under the conditions in which the samples were supplied to the probe by direct infusion at constant flow rates. The presence of ACN prevents the formation of methanol adducts such as [M + MeOH + H](+) and [M + MeOH + Na](+), while also lowering the signal intensity of sodiated [M + Na](+) ions. Sensitivity of these signaling molecules in terms of signal-to-noise ratio (S/N) using low-resolution LTQ-MS and high-resolution FTICR-MS were compared under reversed-phase (RP) LC separations with ESI interface. Special emphasis was paid to the choice of the separation column, its elution conditions and detection of the major AHL compounds produced by the Serratia liquefaciens strain ATCC 27592. The most promising results were obtained using a RP C16-amide column eluted with a linear mobile phase gradient ACN/H(2)O containing 0.1% formic acid. The whole set of AHL homologs in bacterial extracts was detected in the extracted-ion chromatographic (XIC) mode, and the calculations of molecular formulae were performed by including the isotopic pattern. This mode of displaying data, with a very narrow mass-to-charge ratio window (i.e. +/- 0.0010 as m/z unit) around each selected ion, has allowed the identification of all the eight known homoserine lactones, viz. C(4)-HSL, 3-oxo-C(6)-HSL, C(6)-HSL, 3-oxo-C(8)-HSL, C(8)-HSL, C(10)-HSL, C(12)-HSL and C(14)-HSL. In addition, at least four uncommon signaling mediators previously unreported, namely, 3-oxo-C(10:1)-HSL, 3-oxo-C(11:2)-HSL, 3-oxo-C(13:2)-HSL and 3-OH-C(16)-HSL, were identified and characterized; their roles in cell-to-cell communication has to be elucidated.