Coumarinylmethyl Caging Groups with Redshifted Absorption

The small and synthetically easily accessible coumarinylmethyl backbone has been modified to generate a family of photolabile protecting groups with redshifted absorption. We relied on introducing electron‐donating groups in the 7 position and electron‐withdrawing groups in the 2‐, and 2‐ and 3 positions. In particular, we showed that the diethylamino‐thiocoumarylmethyl and the diethylamino‐coumarylidenemalononitrilemethyl are relevant for uncaging with cyan light. They both exhibit a significant action cross section for uncaging in the 470–500 nm wavelength range and a low light absorption between 350 and 400 nm. These attractive features are favorable to perform chromatic orthogonal photoactivation with UV and blue‐cyan light sources, respectively.     

Tetrahedral onsager crosses for solubility improvement and crystallization bypass

Pure organic molecules exhibiting a suitable concave rigid shape are expected to give porous glasses in the solid state. Such a feature opens new opportunities to avoid crystallization and to improve molecular solubility in relation to the high internal energy of these solid phases. To quantitatively explore the latter strategy, a series of rigid tetrahedral conjugated molecules nC and the corresponding models nR have been synthesized. Related to the present purpose, several properties have been investigated using UV absorption, steady-state fluorescence emission, differential scanning calorimetry, (1)H NMR translational self-diffusion, magic angle spinning (13)C NMR, and multiple-beam interferometry experiments. The present tetrahedral crosses are up to 8 orders of magnitude more soluble than the corresponding model compounds after normalization to the same molecular length. In addition, they give concentrated monomeric solutions that can be used to cover surfaces with homogeneous films whose thickness goes down to the nanometer range. Such attractive features make cross-like molecular architectures promising for many applications.     

Optical pumping and a nondestructive readout of a single magnetic impurity spin in an InAs/GaAs quantum dot

We report on the resonant optical pumping of the | ± 1? spin states of a single Mn dopant in an InAs/GaAs quantum dot which is embedded in a charge tunable device. The experiment relies on a W scheme of transitions reached when a suitable longitudinal magnetic field is applied. The optical pumping is achieved via the resonant excitation of the central Λ system at the neutral exciton X(0) energy. For a specific gate voltage, the redshifted photoluminescence of the charged exciton X- is observed, which allows a nondestructive readout of the spin polarization. An arbitrary spin preparation in the | + 1? or |-1? state characterized by a polarization near or above 50% is evidenced.     

NMR time reversal as a probe of incipient turbulent spin dynamics

We demonstrate time reversal of nuclear spin dynamics in highly magnetized dilute liquid (3)He-(4)He mixtures through effective inversion of long-range dipolar interactions. These experiments, which involve using magic sandwich NMR pulse sequences to generate spin echoes, probe the spatiotemporal development of turbulent spin dynamics and promise to serve as a versatile tool for the study and control of dynamic magnetization instabilities. We also show that a repeated magic sandwich pulse sequence can be used to dynamically stabilize modes of nuclear precession that are otherwise intrinsically unstable. To date, we have extended the effective precession lifetimes of our magnetized samples by more than three orders of magnitude.     

Alcohol uncaging with fluorescence reporting: evaluation of o-acetoxyphenyl methyloxazolone precursors

This paper evaluates a series of photolabile protecting groups with built-in fluorescence reporting. They rely on readily available o-acetoxyphenyl methyloxazolones as activated precursors. Alcohol substrates are easily caged. The resulting photoactivable esters exhibit large one- and two-photon uncaging cross sections. The alcohol substrates are quantitatively released in a 1:1 molar ratio with a strongly fluorescent coumarin coproduct that serves as a reporter to quantify substrate delivery.     

Isolation of human haemoglobin variants with altered Bohr effect. Application to haemoglobin Rainier

Isoelectric focusing on polyacrylamide gel in the absence of haem ligands represents a useful, convenient and rapid procedure to isolate silent Hb variants in their native forms, provided that they exhibit an abnormal Bohr effect. The amount of material which is eluted is sufficient for both a limited functional study and a structural determination using microscale high-performance liquid chromatography. This is exemplified by the isolation and the study of Hb Rainier.     

Dosage de l'azote dans le vanadium par fusion reductrice sous vide

A study of the conditions for the determination of nitrogen in vanadium by vacuum fusion in a platinum bath has shown that (a) the amount of nitrogen extracted depends on the ratio (R) of the weights of platinum and vanadium, and (b) the amount extracted passes through a maximum value for a particular R value depending on the temperature. With R values of ca. 2 and extraction temperatures above 1900°, results were in reasonable agreement with those obtained by the Kjeldahl method, the reproducibility being 2–3%.     

Electron donor-acceptor dyads and triads based on tris(bipyridine)ruthenium(II) and benzoquinone: synthesis,characterization, and photoinduced electron transfer reactions

Two electron donor-acceptor triads based on a benzoquinone acceptor linked to a light absorbing [Ru(bpy)(3)](2+) complex have been synthesized. In triad 6 (denoted Ru(II)-BQ-Co(III)), a [Co(bpy)(3)](3+) complex, a potential secondary acceptor, was linked to the quinone. In the other triad, 8 (denoted PTZ-Ru(II)-BQ), a phenothiazine donor was linked to the ruthenium moiety. The corresponding dyads Ru(II)-BQ (4) and PTZ-Ru(II) (9) were prepared for comparison. Upon light excitation in the visible band of the ruthenium moiety, electron transfer to the quinone occurred with a rate constant k(f) = 5 x 10(9) s(-)(1) (tau(f) = 200 ps) in all the quinone containing complexes. Recombination to the ground state followed, with a rate constant k(b) approximately 4.5 x 10(8) s(-)(1) (tau(b) approximately 2.2 ns), for both Ru(II)-BQ and Ru(II)-BQ-Co(III) with no indication of a charge shift to generate the reduced Co(II) moiety. In the PTZ-Ru(II)-BQ triad, however, the initial charge separation was followed by a rapid (k > 5 x 10(9) s(-)(1)) electron transfer from the phenothiazine moiety to give the fairly long-lived PTZ(*)(+)-Ru(II)-BQ(*)(-) state (tau = 80 ns) in unusually high yield for a [Ru(bpy)(3)](2+)-based triad (> 90%), that lies at DeltaG degrees = 1.32 eV relative to the ground state. Unfortunately, this triad turned out to be rather photolabile. Interestingly, coupling between the oxidized PTZ(*)(+) and the BQ(*)(-) moieties seemed to occur. This discouraged further extension to incorporate more redox active units. Finally, in the dyad PTZ-Ru(II) a reversible, near isoergonic electron transfer was observed on excitation. Thus, a quasiequilibrium was established with an observed time constant of 7 ns, with ca. 82% of the population in the PTZ-Ru(II) state and 18% in the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state. These states decayed in parallel with an observed lifetime of 90 ns. The initial electron transfer to form the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state was thus faster than what would have been inferred from the Ru(II) emission decay (tau = 90 ns). This result suggests that reports for related PTZ-Ru(II) and PTZ-Ru(II)-acceptor complexes in the literature might need to be reconsidered.