Chromium complexes for luminescence, solar cells, photoredox catalysis, upconversion, and phototriggered NO release

Some complexes of Cr(III) and Cr(0) have long been known to exhibit interesting photophysical and photochemical properties, but in the past few years important conceptual progress was made. This Perspective focuses on the recent developments of Cr(III) complexes as luminophores and dyes for solar cells, their application in photoredox catalysis, their use as sensitizers in upconversion processes, and their performance as photochemical nitric oxide sources. The example of a luminescent Cr(0) isocyanide complex illustrates the possibility of obtaining photoactive analogues of d6 metal complexes that are commonly made from precious metals such as Ru(II) or Ir(III). The studies highlighted herein illustrate the favorable excited-state properties of robust first-row transition metal complexes with broad application potential

Untangling the Recombination Line Emission from HII Regions with Multiple Velocity Components

HII regions are the ionized spheres surrounding high-mass stars. They are ideal targets for tracing Galactic structure because they are predominantly found in spiral arms and have high luminosities at infrared and radio wavelengths. In the Green Bank Telescope HII Region Discovery Survey (GBT HRDS) we found that >30% of first Galactic quadrant HII regions have multiple hydrogen radio recombination line (RRL) velocities, which makes determining their Galactic locations and physical properties impossible. Here we make additional GBT RRL observations to determine the discrete HII region velocity for all 117 multiple-velocity sources within 18deg. < l < 65deg. The multiple-velocity sources are concentrated in the zone 22deg. < l < 32deg., coinciding with the largest regions of massive star formation, which implies that the diffuse emission is caused by leaked ionizing photons. We combine our observations with analyses of the electron temperature, molecular gas, and carbon recombination lines to determine the source velocities for 103 discrete H II regions (88% of the sample). With the source velocities known, we resolve the kinematic distance ambiguity for 47 regions, and thus determine their heliocentric distances.Comment: 44 pages, 5 figures, 16 pages of tables; Accepted by ApJ

A closer look at ARSA activity in a patient with metachromatic leukodystrophy.

Metachromatic leukodystrophy (MLD) is an autosomal recessive lysosomal storage disease mainly caused by a deficiency of arylsulfatase A activity. The typical clinical course of patients with the late infantile form includes a regression in motor skills with progression to dysphagia, seizures, hypotonia and death. We present a case of a 4-year-old female with rapidly progressive developmental regression with loss of motor milestones, spasticity and dysphagia. MRI showed volume loss and markedly abnormal deep white matter. Enzymatic testing in one laboratory showed arylsulfatase A activity in their normal range. However, extraction of urine showed a large increase in sulfatide excretion in a second laboratory. Measurement of arylsulfatase A in that laboratory showed a partial decrease in arylsulfatase A activity measured under typical conditions (about 37% of the normal mean). When the concentration of substrate in the assay was lowered to one quarter of that normally used, this individual had activity \u3c10% of controls. The patient was found to be homozygous for an unusual missense mutation in the arylsulfatase A gene confirming the diagnosis of MLD. This case illustrates the importance of careful biochemical and molecular testing for MLD if there is suspicion of this diagnosis

Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion

Many CuI complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic ZnII compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet π–π* states. We report two closely related tetrahedral ZnII compounds, in which intersystem crossing occurs with appreciable quantum yields and leads to the population of triplet excited states with intraligand charge-transfer (ILCT) character. In addition to showing fluorescence from their initially excited 1ILCT states, these new compounds therefore undergo triplet–triplet energy transfer (TTET) from their 3ILCT states and consequently can act as sensitizers for photo-isomerization reactions and triplet–triplet annihilation upconversion from the blue to the ultraviolet spectral range. The photoactive 3ILCT state furthermore facilitates photoinduced electron transfer. Collectively, our findings demonstrate that mononuclear ZnII compounds with photophysical and photochemical properties reminiscent of well-known CuI complexes are accessible with suitable ligands and that they are potentially amenable to many different applications. Our insights seem relevant in the greater context of obtaining photoactive compounds based on abundant transition metals, complementing well-known precious-metal-based luminophores and photosensitizers

An Ontological Approach to XBRL Financial Statement Reporting

As a standard for the exchange, transmission, and reporting of accounting and financial data, XRBL goes a long way towardstandardization. However, as the extent of contemporary financial markets is now global, XBRL reporting must transcend oraccommodate differences in reporting standards. While XBRL has been of great help in standardizing the presentation of theU.S. GAAP and IASB standards, reconciling meaning between these standards is still a manual and error-prone affair. As awide variety of stakeholders, spanning countries and cultures, will likely take part in digesting XBRL-formatted financialreports; how will they participate at an appropriate level that is meaningful for them? This paper focuses on an ontologicalapproach towards solving this problem by offering an XBRL ontology architecture for translation between XBRL formats.The architecture is explained, evaluation criteria offered, and future research towards realizing artifacts which use thisarchitecture are proffered

High p_T Triggered Delta-eta,Delta-phi Correlations over a Broad Range in Delta-eta

The first measurement of pseudorapidity (Delta-eta) and azimuthal angle (Delta-phi) correlations between high transverse momentum charged hadrons (p_T > 2.5 GeV/c) and all associated particles is presented at both short- (small Delta-eta) and long-range (large Delta-eta) over a continuous pseudorapidity acceptance (-4<Delta-eta<2). In these proceedings, the various near- and away-side features of the correlation structure are discussed as a function of centrality in Au+Au collisions measured by PHOBOS at sqrt(s_NN)=200 GeV. In particular, this measurement allows a much more complete determination of the longitudinal extent of the ridge structure, first observed by the STAR collaboration over a limited eta range. In central collisions the ridge persists to at least Delta-eta=4, diminishing in magnitude as collisions become more peripheral until it disappears around Npart=80.Comment: 5 pages, 2 figures, presented at the 20th International Conference on Ultra-Relativistic Nucleus-Nucleus Collisions, "Quark Matter 2008", Jaipur, India, February 4-10, 2008. Full author list included and typo corrected in equation

A Molybdenum(0) Isocyanide Analogue of [Ru(2,2'-Bipyridine)3]2+: Strong Reductant for Photoredox Catalysis

We report the first homoleptic Mo0 complex with bidentate isocyanide ligands, which exhibits metal-to-ligand charge transfer (3MLCT) luminescence with quantum yields and lifetimes similar to Ru(bpy)32+ (bpy=2,2′-bipyridine). This Mo0 complex is a very strong photoreductant, which manifests in its capability to reduce acetophenone with essentially diffusion-limited kinetics as shown by time-resolved laser spectroscopy. The application potential of this complex for photoredox catalysis was demonstrated by the rearrangement of an acyl cyclopropane to a 2,3-dihydrofuran, which is a reaction that requires a reduction potential so negative that even the well-known and strongly reducing Ir(2-phenylpyridine)3 photosensitizer cannot catalyze it. Our study thus provides the proof-of-concept for the use of chelating isocyanides to obtain Mo0 complexes with long-lived 3MLCT excited states that are applicable to unusually challenging photoredox chemistry