Series of Near-IR-Absorbing Transition Metal Complexes with Redox Active Ligands.

New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications.

Submillisecond hyperpolarization of nuclear spins in silicon.

In this Letter, we devise a fast and effective nuclear spin hyperpolarization scheme, which is, in principle, magnetic field independent. We use this scheme to experimentally demonstrate polarizations of up to 66% for phosphorus donor nuclear spins in bulk silicon, which are created within less than 100 µs in a magnetic field of 0.35 T at a temperature of 5 K. The polarization scheme is based on a spin-dependent recombination process via weakly coupled spin pairs, for which the recombination time constant strongly depends on the relative orientation of the two spins. We further use this scheme to measure the nuclear spin relaxation time and find a value of ∼100 ms under illumination, in good agreement with the value calculated for nuclear spin flips induced by repeated ionization and deionization processes.

Coherent storage of photoexcited triplet states using 29Si nuclear spins in silicon.

Pulsed electron paramagnetic resonance spectroscopy of the photoexcited, metastable triplet state of the oxygen-vacancy center in silicon reveals that the lifetime of the m(s)=±1 sublevels differs significantly from that of the m(s)=0 state. We exploit this significant difference in decay rates to the ground singlet state to achieve nearly ~100% electron-spin polarization within the triplet. We further demonstrate the transfer of a coherent state of the triplet electron spin to, and from, a hyperfine-coupled, nearest-neighbor (29)Si nuclear spin. We measure the coherence time of the (29)Si nuclear spin employed in this operation and find it to be unaffected by the presence of the triplet electron spin and equal to the bulk value measured by nuclear magnetic resonance.

In control?: Ukrainian opiate substitution treatment patients strive for a voice in their treatment.

This article explores the burgeoning advocacy movement for methadone and buprenorphine treatment by patients, parents, and doctors in Ukraine, and their efforts to remake a system that infantilizes and controls patients into one where patients have a voice in their treatment. Through a review of gray literature and in-depth interviews with 28 patient-advocates and doctors in five Ukrainian cities between October 2009 and July 2010, this piece chronicles the emergence of opiate substitution treatment in Ukraine, describes successes toward patient-friendly treatment, and explores the institutionalized barriers that have pushed the patients to become advocates for their own treatment.