Radiative corrections to the decay τ → Mντ

The electromagnetic corrections to τ → Mν_τ decay, where M is pseudoscalar meson, are treated with all generality. An expression for the decay rate is found, which is accurate up to a few hundredths of a percent, provided hard bremsstrahlung photons are discriminated.     

Harmonic balance approach to the periodic solutions of the (an)harmonic relativistic oscillator

The first-order harmonic balance method via the first Fourier coefficient is used to construct two approximate frequency-amplitude relations for the relativistic oscillator for which the nonlinearity (anharmonicity) is a relativistic effect due to the time line dilation along the world line. Making a change of variable, a new nonlinear differential equation is obtained and two procedures are used to approximately solve this differential equation. In the first the differential equation is rewritten in a form that does not contain a square-root expression, while in the second the differential equation is solved directly. The approximate frequency obtained using the second procedure is more accurate than the frequency obtained with the first due to the fact that, in the second procedure, application of the harmonic balance method produces an infinite set of harmonics, while in the first procedure only two harmonics are produced. Both approximate frequencies are valid for the complete range of oscillation amplitudes, and excellent agreement of the approximate frequencies with the exact one are demonstrated and discussed. The discrepancy between the first-order approximate frequency obtained by means of the second procedure and the exact frequency never exceeds 1.6%. We also obtained the approximate frequency by applying the second-order harmonic balance method and in this case the relative error is as low 0.31% for all the range of values of amplitude of oscillation A.     

A reduction technique for discrete generalized algebraic and difference Riccati equations

This paper proposes a reduction technique for the generalized Riccati difference equation arising in optimal control and optimal filtering. This technique relies on a study on the generalized discrete algebraic Riccati equation. In particular, an analysis on the eigenstructure of the corresponding extended symplectic pencil enables to identify a subspace in which all the solutions of the generalized discrete algebraic Riccati equation are coincident. This subspace is the key to derive a decomposition technique for the generalized Riccati difference equation. This decomposition isolates a “nilpotent” part, which converges to a steady-state solution in a finite number of steps, from another part that can be computed by iterating a reduced-order generalized Riccati difference equation.     

Photon emission as a source of coherent behavior of polaritons

We show that the combined effect of photon emission and Coulomb interactions may drive an exciton-polariton system towards a dynamical coherent state, even without phonon thermalization or any other relaxation mechanism. Exact diagonalization results for a finite system (a multilevel quantum dot interacting with the lowest-energy photon mode of a microcavity) are presented in support of this statement.     

Discordant Supramolecular Fibres Reversibly Depolymerised by Temperature and Light

Synthetic stimuli responsive supramolecular polymers attract increasing interest for their ability to mimic the unique properties of natural assemblies. Here we focus on the well-studied benzene-1,3,5-tricarboxamide (BTA) motif, and substitute it with two (S)-3,7-dimethyloctyl groups and an azobenzene photoswitch. We demonstrate the UV (λ=365 nm) induced depolymerisation of the helical hydrogen-bonded polymers in methylcyclohexane (MCH) through circular dichroism and UV-vis spectroscopy in dilute solution (15 μm ), and NMR and iPAINT super-resolution microscopy in concentrated solution (300 μm ). The superstructure can be regenerated after thermal depolymerization, whilst repeated depolymerisation can be reversed without degradation by irradiating at λ=455 nm. Molecular dynamics simulations show that the most energetically favourable configuration for these polymers in MCH is a left-handed helical network of hydrogen-bonds between the BTA cores surrounded by two right-handed helices of azobenzenes. The responsiveness to two orthogonal triggers across a broad concentration range holds promise for use in, for example, photo-responsive gelation.     

Relaxation properties of porphyrin, diprotonated porphyrin, and isoelectronic tetraoxaporphyrin dication in the S2 state

The fluorescence spectra of unsubstituted porphyrin (H2P), diprotonated porphyrin (H4P2+), and isoelectronic tetraoxaporphyrin dication (TOxP2+) have been measured in solution at room temperature. The S2-->S0 fluorescence has been observed, much more intense for TOxP2+ than for H4P2+ and H2P. In the TOxP2+ case, the S2-->S0 fluorescence spectrum is remarkably sharp and shows an excellent mirror symmetry with respect to S0-->S2 absorption. On the contrary, the spectra of H4P2+ and H2P are shifted and more extended with respect to the absorption counterparts. The differences have been attributed primarily to the change of the equilibrium geometry upon excitation, larger in H2P and H4P2+ than in TOxP2+ and in the case of H4P2+ to the nonplanar conformation of the macrocycle. Also the S1-->S0 spectra of H2P, H4P2+, and TOxP2+ have been measured and more qualitatively discussed. The S1 and S2 fluorescence decays have been observed for H4P2+ and TOxP2+ exciting with ultrashort pulses. The S2 lifetime of TOxP2+ is of the order of the temporal resolution of our experimental apparatus, whereas that of H4P2+ is shorter. The S2-->S0 quantum yield of TOxP2+ has been estimated to be 0.035, approximately 3 orders of magnitude higher than that of H4P2+. It is proposed on the basis of ab initio model calculations that excited states of the H4P2+(CF3COO-)2 complex with charge-transfer character are responsible of the increased extension of the S2-->S0 spectrum with respect to that of H2P.     

Fiber introduction mass spectrometry: determination of pesticides in herbal infusions using a novel sol-gel PDMS/PVA fiber for solid-phase microextraction

An application of the direct coupling of solid-phase microextraction (SPME) with mass spectrometry (MS), a technique known as fiber introduction mass spectrometry (FIMS), is described to determine organochlorine (OCP) and organophosphorus (OPP) pesticides in herbal infusions of Passiflora L. A new fiber coated with a composite of poly(dimethylsiloxane) and poly(vinyl alcohol) (PDMS/PVA) was used. Sensitive, selective, simple and simultaneous quantification of several OCP and OPP was achieved by monitoring diagnostic fragment ions of m/z 266 (chlorothalonil), m/z 195 (alpha-endosulfan), m/z 278 (fenthion), m/z 263 (methyl parathion) and m/z 173 (malathion). Simple headspace SPME extraction (25 min) and fast FIMS detection (less than 40 s) of OCP and OPP from a highly complex herbal matrix provided good linearity with correlation coefficients of 0.991-0.999 for concentrations ranging from 10 to 140 ng ml(-1) of each compound. Good accuracy (80 to 110%), precision (0.6-14.9%) and low limits of detection (0.3-3.9 ng ml(-1)) were also obtained. Even after 400 desorption cycles inside the ionization source of the mass spectrometer, no visible degradation of the novel PDMS/PVA fiber was detected, confirming its suitability for FIMS. Fast (ca 20 s) pesticide desorption occurs for the PDMS/PVA fiber owing to the small thickness of the film and its reduced water sorption.     

Fiber introduction mass spectrometry: determination of pesticides in herbal infusions using a novel sol-gel PDMS/PVA fiber for solid-phase microextraction

An application of the direct coupling of solid-phase microextraction (SPME) with mass spectrometry (MS), a technique known as fiber introduction mass spectrometry (FIMS), is described to determine organochlorine (OCP) and organophosphorus (OPP) pesticides in herbal infusions of Passiflora L. A new fiber coated with a composite of poly(dimethylsiloxane) and poly(vinyl alcohol) (PDMS/PVA) was used. Sensitive, selective, simple and simultaneous quantification of several OCP and OPP was achieved by monitoring diagnostic fragment ions of m/z 266 (chlorothalonil), m/z 195 (alpha-endosulfan), m/z 278 (fenthion), m/z 263 (methyl parathion) and m/z 173 (malathion). Simple headspace SPME extraction (25 min) and fast FIMS detection (less than 40 s) of OCP and OPP from a highly complex herbal matrix provided good linearity with correlation coefficients of 0.991-0.999 for concentrations ranging from 10 to 140 ng ml(-1) of each compound. Good accuracy (80 to 110%), precision (0.6-14.9%) and low limits of detection (0.3-3.9 ng ml(-1)) were also obtained. Even after 400 desorption cycles inside the ionization source of the mass spectrometer, no visible degradation of the novel PDMS/PVA fiber was detected, confirming its suitability for FIMS. Fast (ca 20 s) pesticide desorption occurs for the PDMS/PVA fiber owing to the small thickness of the film and its reduced water sorption.     

Sampling of slow diffusive conformational transitions with accelerated molecular dynamics

Slow diffusive conformational transitions play key functional roles in biomolecular systems. Our ability to sample these motions with molecular dynamics simulation in explicit solvent is limited by the slow diffusion of the solvent molecules around the biomolecules. Previously, we proposed an accelerated molecular dynamics method that has been shown to efficiently sample the torsional degrees of freedom of biomolecules beyond the millisecond timescale. However, in our previous approach, large-amplitude displacements of biomolecules are still slowed by the diffusion of the solvent. Here we present a unified approach of efficiently sampling both the torsional degrees of freedom and the diffusive motions concurrently. We show that this approach samples the configuration space more efficiently than normal molecular dynamics and that ensemble averages converge faster to the correct values.