Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems

Photoswitches and dyes in the liquid-crystalline nematic phase have the potential for use in a wide range of applications. A large order parameter is desirable to maximize the change in properties induced by an external stimulus. A set of photochromic and nonphotochromic dyes were investigated for these applications. It was found that a bent-shaped 7-substituted dihydroazulene (DHA) photoswitch exhibited liquid-crystalline properties. Further investigation demonstrated that this material actually followed two distinct reaction pathways on heating, to a deactivated form by a 1,5-sigmatropic shift and to a linear 6-substituted DHA. In addition, elimination of hydrogen cyanide from the photoactive DHA gave both bent and linear azulene dyes. In a nematic host that has no absorbance around 350 nm, it was found that only the linear DHA derivative has nematic properties; however, both 6- and 7-substituted DHAs were found to have large order parameters. In the nematic host, ring opening of either DHA to the corresponding vinylheptafulvene resulted in a decrease in dichroic order parameter and an unusually fast back-reaction to a mixture of both DHAs. Likewise, only the linear azulene derivative showed mesomorphic properties. In the same nematic host, large order parameters were also observed for these dyes

Quantum Sign Permutation Polytopes

Convex polytopes are convex hulls of point sets in the $n$-dimensional space \E^n that generalize 2-dimensional convex polygons and 3-dimensional convex polyhedra. We concentrate on the class of $n$-dimensional polytopes in \E^n called sign permutation polytopes. We characterize sign permutation polytopes before relating their construction to constructions over the space of quantum density matrices. Finally, we consider the problem of state identification and show how sign permutation polytopes may be useful in addressing issues of robustness

An additive subfamily of enlargements of a maximally monotone operator

We introduce a subfamily of additive enlargements of a maximally monotone operator. Our definition is inspired by the early work of Simon Fitzpatrick. These enlargements constitute a subfamily of the family of enlargements introduced by Svaiter. When the operator under consideration is the subdifferential of a convex lower semicontinuous proper function, we prove that some members of the subfamily are smaller than the classical $\epsilon$-subdifferential enlargement widely used in convex analysis. We also recover the epsilon-subdifferential within the subfamily. Since they are all additive, the enlargements in our subfamily can be seen as structurally closer to the $\epsilon$-subdifferential enlargement

Tracking molecular resonance forms of donor-acceptor push-pull molecules by single-molecule conductance experiments

The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment

Excited States of Proton-bound DNA/RNA Base Homo-dimers: Pyrimidines

We are presenting the electronic photo fragment spectra of the protonated pyrimidine DNA bases homo-dimers. Only the thymine dimer exhibits a well structured vibrational progression, while protonated monomer shows broad vibrational bands. This shows that proton bonding can block some non radiative processes present in the monomer.Comment: We acknowledge the use of the computing facility cluster GMPCS of the LUMAT federation (FR LUMAT 2764

Photophysics of Isolated Rose Bengal Anions

Dye molecules based on the xanthene moiety are widely used as fluorescent probes in bioimaging and technological applications due to their large absorption cross-section for visible light and high fluorescence quantum yield. These applications require a clear understanding of the dye’s inherent photophysics and the effect of a condensed-phase environment. Here, the gas-phase photophysics of the rose bengal doubly deprotonated dianion [RB – 2H]2–, deprotonated monoanion [RB – H]−, and doubly deprotonated radical anion [RB – 2H]•– is investigated using photodetachment, photoelectron, and dispersed fluorescence action spectroscopies, and tandem ion mobility spectrometry (IMS) coupled with laser excitation. For [RB – 2H]2–, photodetachment action spectroscopy reveals a clear band in the visible (450–580 nm) with vibronic structure. Electron affinity and repulsive Coulomb barrier (RCB) properties of the dianion are characterized using frequency-resolved photoelectron spectroscopy, revealing a decreased RCB compared with that of fluorescein dianions due to electron delocalization over halogen atoms. Monoanions [RB – H]− and [RB – 2H]•– differ in nominal mass by 1 Da but are difficult to study individually using action spectroscopies that isolate target ions using low-resolution mass spectrometry. This work shows that the two monoanions are readily distinguished and probed using the IMS-photo-IMS and photo-IMS-photo-IMS strategies, providing distinct but overlapping photodissociation action spectra in the visible spectral range. Gas-phase fluorescence was not detected from photoexcited [RB – 2H]2– due to rapid electron ejection. However, both [RB – H]− and [RB – 2H]•– show a weak fluorescence signal. The [RB – H]− action spectra show a large Stokes shift of ∼1700 cm–1, while the [RB – 2H]•– action spectra show no appreciable Stokes shift. This difference is explained by considering geometries of the ground and fluorescing states

The regeneration capacity of the flatworm Macrostomum lignano—on repeated regeneration, rejuvenation, and the minimal size needed for regeneration

The lion’s share of studies on regeneration in Plathelminthes (flatworms) has been so far carried out on a derived taxon of rhabditophorans, the freshwater planarians (Tricladida), and has shown this group’s outstanding regeneration capabilities in detail. Sharing a likely totipotent stem cell system, many other flatworm taxa are capable of regeneration as well. In this paper, we present the regeneration capacity of Macrostomum lignano, a representative of the Macrostomorpha, the basal-most taxon of rhabditophoran flatworms and one of the most basal extant bilaterian protostomes. Amputated or incised transversally, obliquely, and longitudinally at various cutting levels, M. lignano is able to regenerate the anterior-most body part (the rostrum) and any part posterior of the pharynx, but cannot regenerate a head. Repeated regeneration was observed for 29 successive amputations over a period of almost 12 months. Besides adults, also first-day hatchlings and older juveniles were shown to regenerate after transversal cutting. The minimum number of cells required for regeneration in adults (with a total of 25,000 cells) is 4,000, including 160 neoblasts. In hatchlings only 1,500 cells, including 50 neoblasts, are needed for regeneration. The life span of untreated M. lignano was determined to be about 10 months