Über Rosmarin und Rosmarinsäure

Rosmarinic acid, a tan from Lamiaceae, is found in rosemary and many other plants such as thyme, painted nettle, savory, sage, oregano, or lemon balm, from which it has been isolated here. It is a caffeic acid ester and a chiral, aromatic natural product. Rosmarinic acid tastes bitter, which may be attractive for rosemary as spice. Due to the catechol subunit the acid is an antioxidant. Using rosmarinic acid as a cure is possible due to manyfold physiological effects which are still under investigation. The rosmarinic acid biosynthesis pathway was completely elucidated at the painted nettle. This led to attempts to produce the acid biotechnologically by plant cell cultures in high yields. The preparation of a spectroscopically pure sample is challenging. All analytical spectra were recorded and are reproduced and interpreted either in the main part or in the supporting information.     

A two-particle exchange interaction model

The magnetisation reversal of two interacting particles was investigated within a simple model describing exchange coupling of magnetically uniaxial single-domain particles. Depending on the interaction strength W, the reversal may be cooperative or non-cooperative. A non-collinear reversal mode is obtained even for two particles with parallel easy axes. The model yields different phenomena as observed in spring magnets such as recoil hysteresis in the second quadrant of the field-magnetisation-plane, caused by exchange bias, as well as the mentioned reversal-rotation mode. The Wohlfarth’s remanence analysis performed on aggregations of such pairs of interacting particles shows that the deviation δM(H_m) usually being considered as a hallmark of magnetic interaction vanishes for all maximum applied fields H_m not only at W=0, but also for sufficiently large values of W. Furthermore, this so-called δM-plot depends on whether the sample is ac-field or thermally demagnetised.     

Single‐Molecule Spectroscopy on a Ladder‐Type Conjugated Polymer: Electron–Phonon Coupling and Spectral Diffusion

We employ low‐temperature single‐molecule spectroscopy combined with pattern recognition techniques for data analysis on a methyl‐substituted ladder‐type poly(para‐phenylene) (MeLPPP) to investigate the electron–phonon coupling to low‐energy vibrational modes as well as the origin of the strong spectral diffusion processes observed for this conjugated polymer. The results indicate weak electron–phonon coupling to low‐frequency vibrations of the surrounding matrix of the chromophores, and that low‐energy intrachain vibrations of the conjugated backbone do not couple to the electronic transitions of MeLPPP at low temperatures. Furthermore, these findings suggest that the main line‐broadening mechanism of the zero‐phonon lines of MeLPPP is fast, unresolved spectral diffusion, which arises from conformational fluctuations of the side groups attached to the MeLPPP backbone as well as of the surrounding host material.     

Ionization of noble gases with pulses directly from a laser oscillator

A Ti:sapphire oscillator with an extended cavity generates pulses with 0.5 microJ energy at a repetition rate of 6 MHz and pulse durations of 50 fs. Tight focusing creates peak intensities exceeding 10(14) W/cm2, which is sufficient for ionizing helium, a nonlinear process where at least 17 photons are absorbed simultaneously.     

Preferential oxidative addition in Suzuki cross-coupling reactions across one fluorene unit

The Suzuki-type cross-coupling reaction of 2,7-dihalofluorenes with 1 equiv of arylboronic acid and Pd2(dba)3/P(t-Bu3) as a catalyst system is investigated. The exclusive formation of the diarylated coupling product demonstrates that "preferential oxidative addition" is also applicable to fluorene monomers due to a controlled intramolecular motion of the regenerated Pd(0) catalyst across the "large" distance between the 2- and the 7-position of one fluorene monomer.     

Spatiotemporal imaging of ultrafast molecular motion: collapse and revival of the D+2 nuclear wave packet

We report on a real-time imaging of the ultrafast D(+)2 rovibrational nuclear wave-packet motion performed using a combination of a pump-probe setup with 7 fs laser pulses and a "reaction-microscope" spectrometer. We observe fast dephasing (collapse) of the vibrational wave packet and its subsequent revival and prove rotational excitation in ultrashort laser pulses. Channel-selective Fourier analysis of the wave packet's long-term (approximately 3000 fs) evolution allows us to resolve its individual constituents, revealing unique information on the mechanisms of strong-field ionization and dissociation.     

System Representations for the Paley–Wiener Space $$\mathcal {PW}_{\pi }^2$$

In this paper we study the approximation of stable linear time-invariant systems for the Paley–Wiener space \(\mathcal {PW}_{\pi }^2\), i.e., the set of bandlimited functions with finite \(L^2\)-norm, by convolution sums. It is possible to use either, the convolution sum where the time variable is in the argument of the bandlimited impulse response, or the convolution sum where the time variable is in the argument of the function, as an approximation process. In addition to the pointwise and uniform convergence behavior, the convergence behavior in the norm of the considered function space, i.e. the \(L^2\)-norm in our case, is important. While it is well-known that both convolution sums converge uniformly on the whole real axis, the \(L^2\)-norm of the second convolution sum can be divergent for certain functions and systems. We show that the there exist an infinite dimensional closed subspace of functions and an infinite dimensional closed subspace of systems, such that for any pair of function and system from these two sets, we have norm divergence.     

Wavelength dependence of electronic relaxation in isolated adenine using UV femtosecond time-resolved photoelectron spectroscopy

Electronic relaxation pathways in photoexcited nucleobases have received much theoretical and experimental attention due to their underlying importance to the UV photostability of these biomolecules. Multiple mechanisms with different energetic onsets have been proposed by ab initio calculations yet the majority of experiments to date have only probed the photophysics at a few selected excitation energies. We present femtosecond time-resolved photoelectron spectra (TRPES) of the DNA base adenine in a molecular beam at multiple excitation energies between 4.7-6.2 eV. The two-dimensional TRPES data is fit globally to extract lifetimes and decay associated spectra for unambiguous identification of states participating in the relaxation. Furthermore, the corresponding amplitude ratios are indicative of the relative importance of competing pathways. We adopt the following mechanism for the electronic relaxation of isolated adenine; initially the S(2)(ππ*) state is populated by all excitation wavelengths and decays quickly within 100 fs. For excitation energies below ～5.2 eV, the S(2)(ππ*)→S(1)(nπ*)→S(0) pathway dominates the deactivation process. The S(1)(nπ*)→S(0) lifetime (1032-700 fs) displays a trend toward shorter time constants with increasing excitation energy. On the basis of relative amplitude ratios, an additional relaxation channel is identified at excitation energies above 5.2 eV.     

Microcavity lasing of optically excited cadmium sulfide thin films at room temperature

We report what is believed to be the first observation of lasing of an optically pumped thin CdS film formed by laser ablation on glass. Laser action is observed at room temperature, and the emission peak is at 501 nm. X-ray diffraction shows that the polycrystalline films are of wurtzite structure and have (002) preferred orientation. Fabry-Perot laser modes are spaced 16 nm apart, indicating a cavity length of 2.9mum . The cavity is formed by consistently self-formed microcavities within the hexagonal lattice.