Coarse-graining stiff bonds

The method of constraints in molecular dynamics is useful because it avoids the resolution of high frequency motions with very small time steps. However, the price to pay is that both the dynamics and the statistics of a constrained system differ from those of the unconstrained one. Instead of using constraints, we propose to dispose of high frequency motions by a coarse-graining procedure in which fast variables are eliminated. These fast variables are thus modeled as friction and thermal fluctuations. We illustrate the methodology with a simple model case, a diatomic molecule in a monoatomic solvent, in which the bond between the atoms of a diatomic molecule is stiff. Although the example is very simple and does not display the interesting effects of “wrong” statistics of the constrained system (i.e. the well-known issue connected to the Fixman potential), it is well suited to give the proof of concept of the whole procedure.     

Efficient up-conversion in CdSe

In this work up-conversion in CdSe with a HF laser as a pump and an experimental quantum efficiency higher than 40% is reported. With this device, it is possible to obtain up-conversion in the 8–25 μ wavelength range.     

A picosecond dye laser tunable in the 1.1μ m region

We report in this letter the characteristic of a picosecond dye laser, tunable in the 1.08–1.12 μm range. The dye is pumped by the fundamental of a mode-locked Nd-YAG laser. The energy conversion efficiency is higher than 10% and the pulse duration is less than 10 ps.     

Nonlinear mobility of a driven system: Temperature and disorder effects

We consider the dissipative nonlinear dynamics of a model of interacting atoms driven over a substrate potential. The substrate parameters can be suitably tuned in order to introduce disorder effects starting from two geometrically opposed ideal cases: commensurate and incommensurate interfaces. The role of temperature is also investigated through the inclusion of a stochastic force via a Langevin molecular dynamics approach. Here, we focus on the most interesting tribological case of underdamped sliding dynamics. For different values of the chain stiffness, we evaluate the static friction threshold and consider the depinning transition mechanisms as a function of the applied driving force. As experimentally observed in QCM frictional measurements of adsorbed layers, we find that disorder operates differently depending on the starting geometrical configuration. For commensurate interfaces, randomness lowers considerably the chain depinning threshold. On the contrary, for incommensurate mating contacts, disorder favors static pinning destroying the possible frictionless (superlubric) sliding states. Interestingly, thermal and disorder effects strongly influence also the occurrence of parametric resonances inside the chain, capable of converting the kinetic energy of the center-of-mass motion into internal vibrational excitations. We comment on the nature of the different dynamical states and hysteresis (due to system bi-stability) observed at different increasing and decreasing strengths of the external force.     

Microemulsion electrokinetic chromatography: an application for the simultaneous determination of suspected fragrance allergens in rinse-off products

The feasibility of microwave-accelerated derivatization for capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection was evaluated. The derivatization reaction was performed in a domestic microwave oven. Histidine (His), 1-methylhistidine (1-MH) and 3-methylhistidine (3-MH) were selected as test analytes and fluorescein isothiocyanate (FITC) was chosen as a fluorescent derivatizing reagent. Parameters that may affect the derivatization reaction and/or subsequent CE separation were systematically investigated. Under optimized conditions, the microwave-accelerated derivatization reaction was successfully completed within 150 s, compared to 4-24 h in a conventional water-bath derivatization process. This will remarkably reduce the overall analysis time and increase sample throughput of CE-LIF. The detection limits of this method were found to be 0.023 ng/mL for His, 0.023 ng/mL for 1-MH, and 0.034 ng/mL for 3-MH, respectively, comparable to those obtained using traditional derivatization protocols. The proposed method was characterized in terms of precision, linearity, accuracy and successfully applied for rapid and sensitive determination of these analytes in human urine.     

Symmetry Groups and Non-Planar Collisionless Action-Minimizing Solutions of the Three-Body Problem in Three-Dimensional Space

Periodic and quasi-periodic solutions of the n-body problem can be found as minimizers of the Lagrangian action functional restricted to suitable spaces of symmetric paths. The main purpose of this paper is to develop a systematic approach to the equivariant minimization for the three-body problem in three-dimensional space. First we give a finite complete list of symmetry groups fitting to the minimization of the action, with the property that any other symmetry group can be reduced to be isomorphic to one of these representatives. A second step is to prove that the resulting (local and global) symmetric action-minimizers are always collisionless (when they are not already bound to collisions). Furthermore, we prove some results which address the question of whether minimizers are planar or non-planar; as a consequence of our theory we will give general criteria for a symmetry group to yield planar or homographic minimizers (either homographic or not, as in the Chenciner-Montgomery eight solution). On the other hand we will provide a rigorous proof of the existence of some interesting one-parameter families of periodic and quasi-periodic non-planar orbits. These include the choreographic Marchal's P₁₂ family with equal masses – together with a less-symmetric choreographic family (which anyway probably coincides with the P₁₂ family).     

Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study

Three (donor–π–acceptor)⁺ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials.     

Evaluation of the separation mechanism of electrokinetic chromatography with a microemulsion and cyclodextrins using NMR and molecular modeling

Electrokinetic chromatography (EKC) allows the separation of closely related substances by the detection of fine effects in analyte-separation system interactions. With the goal of understanding the fine effects involved in separation using a dual cyclodextrin-microemulsion EKC system, an integrated study of NMR and molecular modeling was carried out. The above dual cyclodextrin-microemulsion system was previously used in the separation of clemastine and its related substances and was prepared by the addition of methyl-β-cyclodextrin (MβCD) and heptakis(2,6-di-O-methyl)-β-cyclodextrin (DMβCD) to an oil-in-water microemulsion. The use of DMβCD was shown to be essential in the separation of clemastine from one of its related substance (I(B) ). A molecular modeling study allowed the different affinities of clemastine and I(B) for the two cyclodextrins to be explained. Furthermore, rotating-frame Overhauser effect spectroscopy NMR experiments clearly indicated that besides the primary pseudostationary phase, namely the ionic microemulsion, cyclodextrins acted as a secondary pseudostationary phase. In addition, it was shown that inclusion complexation of sodium dodecyl sulfate (SDS) monomers into the cyclodextrins cavity occurs; differently, the oil (n-heptane) used in the preparation of microemulsion system resulted to be not included into the macrocycle cavity. These experimental results were supported by molecular modeling, which highlighted the preferential inclusion of SDS into DMβCD. On the basis of these results, it was confirmed that, besides its primary role as the ionic carrier in EKC, SDS is involved in inclusion equilibria toward CDs, which can be effective in increasing the system selectivity.