Operations on Automata with All States Final

We study the complexity of basic regular operations on languages represented by incomplete deterministic or nondeterministic automata, in which all states are final. Such languages are known to be prefix-closed. We get tight bounds on both incomplete and nondeterministic state complexity of complement, intersection, union, concatenation, star, and reversal on prefix-closed languages.Comment: In Proceedings AFL 2014, arXiv:1405.527

The Power of Solvent in Altering the Course of Photorearrangements

A clean bifurcation between two important photochemical reactions through competition of a triplet state Type II H-abstraction reaction with a photo-Favorskii rearrangement for (o/p)-hydroxy-o-methylphenacyl esters that depends on the water content of the solvent has been established. The switch from the anhydrous Type II pathway that yields indanones to the aqueous-dependent pathway producing benzofuranones occurs abruptly at low water concentrations (~8%). The surprisingly clean yields suggest that such reactions are synthetically promising

Photochemistry of a 9-Dithianyl-Pyronin Derivative: A Cornucopia of Reaction Intermediates Lead to Common Photoproducts

Leaving groups attached to themeso-methyl position of many common dyes, such as xanthene, BODIPY, or pyronin derivatives, can be liberated upon irradiation with visible light. However, the course of phototransformations of such photoactivatable systems can be quite complex and the identification of reaction intermediates or even products is often neglected. This paper exemplifies the photochemistry of a 9-dithianyl-pyronin derivative, which undergoes an oxidative transformation at themeso-position to give a 3,6-diamino-9H-xanthen-9-one derivative, formic acid, and carbon monoxide as the main photoproducts. The course of this multi-photon multi-step reaction was studied under various conditions by steady-state and time-resolved optical spectroscopy, mass spectrometry and NMR spectroscopy to understand the effects of solvents and molecular oxygen on individual steps. Our analyses have revealed the existence of many intermediates and their interrelationships to provide a complete picture of the transformation, which can bring new inputs to a rational design of new photoactivatable pyronin or xanthene derivatives

Photochemistry of Common Xanthene Fluorescent Dyes as Efficient Visible-light Activatable CO-Releasing Molecules

Xanthene derivatives are organic dyes, some of which are routinely used in different chemical and biological applications, including human medicine. In this work, we investigated the photochemistry of some of the most common ones, fluorescein, eosin Y, and rose bengal, and major products of their photodegradation using optical spectroscopy, NMR, chromatography and mass spectroscopy techniques. These substances, usually considered (photo)chemically stable, were found to liberate carbon monoxide (CO) in 40–80% chemical yields upon extensive irradiation with visible light in aqueous solutions during their multistep concomitant degradation processes. In addition, a number of low-mass secondary photoproducts, such as phthalic and formic acids, were identified in the irradiated mixtures. We demonstrate that these common fluorescent dyes can also be considered as visible-light activatable carbon monoxide (CO)-releasing molecules (photoCORMs) under specific conditions with potential biological implications

Fluorescein Analogues as Photoremovable Protecting Groups Absorbing at ∼520 nm

International audienceA new photoremovable protecting group, (6-hydroxy-3-oxo-3H-xanthen-9-yl)methyl (1), with a molar absorption coefficient ε of ∼4 × 104 m–1 cm–1 at ∼520 nm for the release of carboxylates or phosphates is reported. Three derivatives of 1 (diethyl phosphate, acetate, and bromide) were isolated as complexes with DDQ and shown to release the ligands with quantum yields ≤2.4% in aqueous solution

Chemical targeting of voltage sensitive dyes to specific cells and molecules in the brain

Voltage sensitive fluorescent dyes (VSDs) are important tools for probing signal transduction in neurons and other excitable cells. These sensors, rendered highly lipophilic to anchor the conjugated pi-wire molecular framework in the membrane, offer several favorable functional parameters including fast response kinetics and high sensitivity to membrane potential changes. The impact of VSDs has, however, been limited due to the lack of cell-specific targeting methods in brain tissue or living animals. We address this key challenge by introducing a non-genetic molecular platform for cell- and molecule-specific targeting of synthetic voltage sensitive dyes in the brain. We employ a dextran polymer particle to overcome the inherent lipophilicity of voltage sensitive dyes by dynamic encapsulation, and high-affinity ligands to target the construct to specific neuronal cells utilizing only native components of the neurotransmission machinery at physiological expression levels. Dichloropane, a monoamine transporter ligand, enables targeting of dense dopaminergic axons in the mouse striatum and sparse noradrenergic axons in the mouse cortex in acute brain slices. PFQX in conjunction with ligand-directed acyl imidazole chemistry enables covalent labeling of AMPA-type glutamate receptors in the same brain regions. Probe variants bearing either a classical electrochromic ANEP dye or state-of-the-art VoltageFluor-type dye respond to membrane potential changes in a similar manner to the parent dyes, as shown by whole-cell patch recording. We demonstrate the feasibility of optical voltage recording with our probes in brain tissue with one-photon and two-photon fluorescence microscopy and define the signal limits of optical voltage imaging with synthetic sensors under a low photon budget determined by the native expression levels of the target proteins. We envision that modularity of our platform will enable its application to a variety of molecular targets and sensors, as well as lipophilic drugs and signaling modulators. This work demonstrates the feasibility of a chemical targeting approach and expands the possibilities of cell-specific imaging and pharmacology