Synthesis and alkyne-coupling chemistry of cyclomanganated 1- and 3-acetylindoles, 3-formylindole and analogues

The syntheses are reported of new cyclomanganated indole derivatives (1-acetyl-κO-indolyl-κC2)dicarbonylbis(trimethylphosphite)manganese (2), (1-methyl-3-acetyl-κO-indolyl-κC2)tetracarbonylmanganese (4), (3-formyl-κO-indolyl-κC2)tetracarbonylmanganese (5a) and (1-methyl-3-formyl-κO-indolyl-κC2)tetracarbonylmanganese (5b). The unusually complicated crystal structure of 5b has been determined, the first for a cyclomanganated aryl aldehyde. The preparations of a mitomycin-related pyrrolo-indole and related products by thermally promoted and oxidatively (Me3NO) initiated alkyne-coupling reactions of the previously known complex (1-acetyl-κO-indolyl-κC2)tetracarbonylmanganese (1) are reported for different alkynes and solvents. X-ray crystal structures are reported for the dimethyl acetylenedicarboxylate coupling product of 1 (dimethyl 1-methyl-l-hydroxypyrrolo[1,2a]-indole-2,3-dicarboxylate; 6a), and an unusually-cyclised triple insertion product 8 from the coupling of acetylene with 4, in which a cyclopentadiene moiety is η3-allyl-coordinated to Mn through only one double bond and an exocyclic carbon, but which rearranges on heating to an η5-cyclopentadienyl complex

Predicting functional properties of milk powder based on manufacturing data in an industrial-scale powder plant

The fundamental science relating key physical and functional properties of milk powder to plant operating conditions is complex and largely unknown. Consequently this paper takes a data-driven approach to relate the routinely measured plant conditions to one vital function property known as sediment in an industrial-scale powder plant. Data from four consecutive production seasons was examined, and linear regression models based on a chosen set of processing variables were used to predict the sediment values. The average prediction error was well within the range of the uncertainty of the laboratory test. The models could be used to predict the effect of each individual plant variable on the sediment values which could be beneficial in quality optimisation. In addition the choice of the training data set used to compute regression coefficients was studied and the resultant regression models were compared to alternative PLS models built on the same data

VLA Spectral Line Observations of a Shocked Cold H II Region in G70.7+1.2

We have observed the molecular globule G70.7+1.2 at 1375 MHz using the C configuration of the VLA, and have imaged a peculiar H168α recombination line detected at the Arecibo radio telescope. The narrow width of the recombination line (Δv ~ 3 km s-1) indicates gas cooler than 185 K and suggests that the globule harbors the coldest known H II region. Previous work showed that the recombination line came either from newly ionized gas outside a bow shock produced by supersonic motion of an early-type star through the molecular globule, or from a cold H II region inside the globule. The 20'' angular resolution of the VLA image of G70.7+1.2 was sufficient to resolve the separation between the nonthermal radio-emitting bow shock and the thermal H II region. The spectral line images show that the radio recombination line comes from cold gas near the outer boundary of the bow shock and that the line intensity is enhanced by stimulated amplification of the nonthermal continuum emanating from the bow shock

Spatial and Temporal Variations in Small-Scale Galactic HI Structure Toward 3C~138

We present three epochs of VLBA observations of Galactic HI absorption toward the quasar 3C~138 with resolutions of 20 mas (~ 10 AU). This analysis includes VLBA data from observations in 1999 and 2002 along with a reexamination of 1995 VLBA data. Improved data reduction and imaging techniques have led to an order of magnitude improvement in sensitivity compared to previous work. With these new data we confirm the previously detected milliarcsecond scale spatial variations in the HI opacity at the level of Delta(tau_{max}) =0.50 \pm 0.05. The typical size scale of the optical depth variations is ~ 50 mas or 25 AU. In addition, for the first time we see clear evidence for temporal variations in the HI opacity over the seven year time span of our three epochs of data. We also attempted to detect the magnetic field strength in the HI gas using the Zeeman effect. From this analysis we have been able to place a 3 sigma upper limit on the magnetic field strength per pixel of ~45 muG. We have also been able to calculate for the first time the plane of sky covering fraction of the small scale HI gas of ~10%. We also find that the line widths of the milliarcsecond sizescale HI features are comparable to those determined from previous single dish measurements toward 3C~138, suggesting that the opacity variations cannot be due to changes in the HI spin temperature. From these results we favor a density enhancement interpretation for the small scale HI structures, although these enhancements appear to be of short duration and are unlikely to be in equilibrium.Comment: 34 pages, 8 figures. Figures 3 & 4 are in color. Accepted to A

Randomized comparison of the effects of the vitamin D(3 )adequate intake versus 100 mcg (4000 IU) per day on biochemical responses and the wellbeing of patients

BACKGROUND: For adults, vitamin D intake of 100 mcg (4000 IU)/day is physiologic and safe. The adequate intake (AI) for older adults is 15 mcg (600 IU)/day, but there has been no report focusing on use of this dose. METHODS: We compared effects of these doses on biochemical responses and sense of wellbeing in a blinded, randomized trial. In Study 1, 64 outpatients (recruited if summer 2001 25(OH)D <61 nmol/L) were given 15 or 100 mcg/day vitamin D in December 2001. Biochemical responses were followed at subsequent visits that were part of clinical care; 37 patients completed a wellbeing questionnaire in December 2001 and February 2002. Subjects for Study 2 were recruited if their 25(OH)D was <51 nmol/L in summer 2001. 66 outpatients were given vitamin D; 51 completed a wellbeing questionnaire in both December 2002 and February 2003. RESULTS: In Study 1, basal summer 25-hydroxyvitamin D [25(OH)D] averaged 48 ± 9 (SD) nmol/L. Supplementation for more than 6 months produced mean 25(OH)D levels of 79 ± 30 nmol/L for the 15 mcg/day group, and 112 ± 41 nmol/L for the 100 mcg/day group. Both doses lowered plasma parathyroid hormone with no effect on plasma calcium. Between December and February, wellbeing score improved more for the 100-mcg/day group than for the lower-dosed group (1-tail Mann-Whitney p = 0.036). In Study 2, 25(OH)D averaged 39 ± 9 nmol/L, and winter wellbeing scores improved with both doses of vitamin D (two-tail p < 0.001). CONCLUSION: The highest AI for vitamin D brought summertime 25(OH)D to >40 nmol/L, lowered PTH, and its use was associated with improved wellbeing. The 100 mcg/day dose produced greater responses. Since it was ethically necessary to provide a meaningful dose of vitamin D to these insufficient patients, we cannot rule out a placebo wellbeing response, particularly for those on the lower dose. This work confirms the safety and efficacy of both 15 and 100 mcg/day vitamin D(3 )in patients who needed additional vitamin D

The Active Jet in NGC 4258 and Its Associated Shocks

We present images and spectra of the active jet and anomalous arms on subparsec through kiloparsec scales in the LINER/Seyfert galaxy NGC 4258 (M106). New VLBA and multiconfiguration VLA images show that, on 0.3-300 pc scales, the jet in projection aligns with (1) the spin axis of the underlying accretion disk and (2) two radio hot spots 24'' S (840 pc) and 49'' N (1.7 kpc) from the nucleus. Hubble Space Telescope WFPC2 [N II] λ6583 + Hα images locate interactions between the jet and the interstellar medium (ISM). The most prominent is a pair of emission line arcs whose apices face away from the galaxy nucleus and envelop the leading edges of the radio hot spots. Ground-based (WHT) spectra with 2 Å resolution confirm that the gaseous kinematics and excitation of both arcs have the spatio-kinematic structure expected for jet working surfaces with a shock velocity 350 ± 100 km s-1. The north shock is oblique and may lie in a nuclear ionization cone. The south shock shows a detached, putative Mach disk. Models suggest that the S shock is a bow shock around a jet whose progress toward us through the galaxy ISM has stalled. This is notable because the inferred outflow axis is misaligned by ~65° (in three dimensions) with the spin axis of the accretion disk. Our emission line ratios and profiles diagnose the physical properties of the shocks, possible Mach disk, and thence the jets. The shocks lie at one end of a swath of kinematically disturbed gas that reaches back to the previously recognized spiral "anomalous arms," suggesting that they are linked dynamically by precession of the central engine; although claimed elsewhere to be bar shocks, the anomalous arms are probably a fossil record of changing jet activity in NGC 4258. Our results imply that the jet has recently moved a long way out of the plane of the galaxy. A deep Taurus Tunable Filter Hα image shows that discrete strands in the anomalous arms persist to galactocentric radii of at least 4' (>8 kpc), indicating an ongoing ISM interaction

The Nature of the Massive Young Stars in W75 N

We have observed the W75 N massive star forming region in SiO(J=2-1 & J=1-0) at 3" - 5" resolution and in 6 cm, 2 cm, and 7 mm continuum emission at 1.4" - 0.2" resolution. The abundance ratio of [SiO]/[H2] is roughly 5-7 x 10^-11 which is typical for what is expected in the ambient component of molecular clouds with active star formation. The SiO morphology is diffuse and centered on the positions of the ultracompact HII regions - no collimated, neutral jet was discovered. The ionized gas surrounding the protostars have emission measures ranging from 1-15 x 10^6 pc cm^-6, densities from 0.4-5 x 10^4 cm^-3, and derived spectral types of the central ionizing stars ranging from B0.5 to B2. Most of the detected sources have spectral indicies which suggest optically thin to moderately optically thick HII regions produced by a central ionizing star. The spread in ages between the oldest and youngest early-B protostars in the W75 N cluster is 0.1-5 x 10^6 years. This evolutionary timescale for W75 N is consistent with that found for early-B stars born in clusters forming more massive stars (Mstar > 25 Msun).Comment: Astrophysical Journal, in press. 11 pages plus 6 figures (jpg format). See http://www.aoc.nrao.edu/~dshepher/science.shtml for reprint with full resolution figure

Communities, psychotherapeutic innovation and the diversity of international qualitative research in mental health

The articles in this special issue are hugely varied in terms of their country of origin (Brazil, Finland, Italy, Malaysia and the UK); theoretical influences (e.g. Lacanian theory, cultural-historical approaches and relational theories) and method of qualitative analysis (e.g. content and thematic analyses, Lacanian discourse analysis, Grounded theory, ethnography and auto-ethnography). In this commentary, I will discuss each article in turn before moving on to address some common issues including: the relationship between therapeutic innovation and research; differing implicit models of subjectivity; the need for theoretically pluralistic approaches to interpretation; and the need to incorporate the views of service users