Solvent effects in the hydrogenation of 2-butanone

In liquid-phase reaction systems, the role of the solvent is often limited to the simple requirement of dissolving and/or diluting substrates. However, the correct choice, either pure or mixed, can significantly influence both reaction rate and selectivity. For multi-phase heterogeneously catalysed reactions observed variations may be due to changes in mass transfer rates, reaction mechanism, reaction kinetics, adsorption properties and combinations thereof. The liquid-phase hydrogenation of 2-butanone to 2-butanol over a Ru/SiO catalyst, for example, shows such complex rate behaviour when varying water/isopropyl alcohol (IPA) solvent ratios. In this paper, we outline a strategy which combines measured rate data with physical property measurements and molecular simulation in order to gain a more fundamental understanding of mixed solvent effects for this heterogeneously catalysed reaction. By combining these techniques, the observed complex behaviour of rate against water fraction is shown to be a combination of both mass transfer and chemical effects. © 2012 Elsevier Inc. All rights reserved.

Inducing late phase of infarct protection in skeletal muscle by remote preconditioning:efficacy and mechanism

We have previously demonstrated that remote ischemic preconditioning (IPC) by instigation of three cycles of 10-min occlusion/reperfusion in a hindlimb of the pig elicits an early phase of infarct protection in local and distant skeletal muscles subjected to 4 h of ischemia immediately after remote IPC. The aim of this project was to test our hypothesis that hindlimb remote IPC also induces a late phase of infarct protection in skeletal muscle and that K(ATP) channels play a pivotal role in the trigger and mediator mechanisms. We observed that pig bilateral latissimus dorsi (LD) muscle flaps sustained 46 +/- 2% infarction when subjected to 4 h of ischemia/48 h of reperfusion. The late phase of infarct protection appeared at 24 h and lasted up to 72 h after hindlimb remote IPC. The LD muscle infarction was reduced to 28 +/- 3, 26 +/- 1, 23 +/- 2, 24 +/- 2 and 24 +/- 4% at 24, 28, 36, 48 and 72 h after remote IPC, respectively (P <0.05; n = 8). In subsequent studies, hindlimb remote IPC or intravenous injection of the sarcolemmal K(ATP) (sK(ATP)) channel opener P-1075 (2 microg/kg) at 24 h before 4 h of sustained ischemia (i.e., late preconditioning) reduced muscle infarction from 43 +/- 4% (ischemic control) to 24 +/- 2 and 19 +/- 3%, respectively (P <0.05, n = 8). Intravenous injection of the sK(ATP) channel inhibitor HMR 1098 (6 mg/kg) or the nonspecific K(ATP) channel inhibitor glibenclamide (Glib; 1 mg/kg) at 10 min before remote IPC completely blocked the infarct- protective effect of remote IPC in LD muscle flaps subjected to 4 h of sustained ischemia at 24 h after remote IPC. Intravenous bolus injection of the mitochondrial K(ATP) (mK(ATP)) channel inhibitor 5-hydroxydecanoate (5-HD; 5 mg/kg) immediately before remote IPC and 30-min intravenous infusion of 5-HD (5 mg/kg) during remote IPC did not affect the infarct-protective effect of remote IPC in LD muscle flaps. However, intravenous Glib or 5-HD, but not HMR 1098, given 24 h after remote IPC completely blocked the late infarct-protective effect of remote IPC in LD muscle flaps. None of these drug treatments affected the infarct size of control LD muscle flaps. The late phase of infarct protection was associated with a higher (P <0.05) muscle content of ATP at the end of 4 h of ischemia and 1.5 h of reperfusion and a lower (P <0.05) neutrophilic activity at the end of 1.5 h of reperfusion compared with the time-matched control. In conclusion, these findings support our hypothesis that hindlimb remote IPC induces an uninterrupted long (48 h) late phase of infarct protection, and sK(ATP) and mK(ATP) channels play a central role in the trigger and mediator mechanism, respectively.

Auditory false perceptions are mediated by psychosis risk factors

Introduction. Auditory hallucinations exist in psychotic disorders as well as the general population. Proneness to hallucinations, as measured by positive schizotypy, predicts false perceptions during an auditory signal detection task (Barkus, Stirling, Hopkins, McKie, & Lewis, 2007). Our aim was to replicate this result and extend it by examining effects of age and sex, both important demographic predictors of psychosis.

Method. A sample of 76 healthy volunteers split into 15-17 years (n = 46) and 19 years plus (n = 30) underwent a signal detection task designed to detect propensity towards false perceptions under ambiguous auditory conditions. Scores on the Unusual Experiences subscale (UE) of the O-LIFE schizotypy scale, IQ, and a measure of working memory were also assessed.

Results. We replicated our initial finding (Barkus et al., 2007): High scores on positive schizotypy were associated with false perceptions. Younger participants who scored highly on positive schizotypy reported significantly more false perceptions compared to other groups (p = .04). Older participants who had had an imaginary friend reported more false perceptions during the signal detection task (p <. 01).

Conclusions. Younger participants seem most vulnerable to the effects of positive schizotypal traits in terms of a signal detection deficit that underlies auditory hallucinations. Schizotypy may have greatest impact closer to the risk period for development of psychotic disorders.

Behavioral responses to pain are heightened after clustered care in preterm infants born between 30 and 32 weeks gestational age

To compare biobehavioral pain responses of preterm infants born at differing gestational ages (GAs) when pain was preceded by a rest period or by a series of routine nursing interventions.

The Association of Skin-Intrinsic Fluorescence With Type 1 Diabetes Complications in the DCCT/EDIC Study

OBJECTIVESTo determine whether skin-intrinsic fluorescence (SIF) is associated with long-term complications of type 1 diabetes (T1D) and, if so, whether it is independent of chronic glycemic exposure and previous intensive therapy.RESEARCH DESIGN AND METHODSWe studied 1,185 (92%) of 1,289 active Diabetes Control and Complications Trial (DCCT)/Epidemiology of Diabetes Interventions and Complications (EDIC) participants from 2010 to 2011. SIF was determined using a fluorescence spectrometer and related cross-sectionally to recently determined measures of retinopathy (stereo fundus photography), cardiac autonomic neuropathy (CAN; R-R interval), confirmed clinical neuropathy, nephropathy (albumin excretion rate [AER]), and coronary artery calcification (CAC).RESULTSOverall, moderately strong associations were seen with all complications, before adjustment for mean HbA1c over time, which rendered these associations nonsignificant with the exception of sustained AER >30 mg/24 h and CAC, which were largely unaffected by adjustment. However, when examined within the former DCCT treatment group, associations were generally weaker in the intensive group and nonsignificant after adjustment, while in the conventional group, associations remained significant for CAN, sustained AER >30 mg/24 h, and CAC even after mean HbA1c adjustment.CONCLUSIONSSIF is associated with T1D complications in DCCT\EDIC. Much of this association appears to be related to historical glycemic exposure, particularly in the previously intensively treated participants, in whom adjustment for HbA1c eliminates statistical significance.

Modern-day clinical course of type 1 diabetes mellitus after 30 years' duration:the diabetes control and complications trial/epidemiology of diabetes interventions and complications and Pittsburgh epidemiology of diabetes complications experience (1983-2005)

Clinical treatment goals of type 1 diabetes mellitus (T1DM) have changed since the Diabetes Control and Complications Trial (DCCT) demonstrated reduced long-term complications with intensive diabetes therapy. There have been few longitudinal studies to describe the clinical course of T1DM in the age of intensive therapy. Our objective was to describe the current-day clinical course of T1DM.

Ages of 24 widespread tephras erupted since 30,000 years ago in New Zealand, with re-evaluation of the timing and palaeoclimatic implications of the Lateglacial cool episode recorded at Kaipo bog

Tephras are important for the NZ-INTIMATE project because they link all three records comprising the composite inter-regional stratotype developed for the New Zealand climate event stratigraphy (NZ-CES). Here we firstly report new calendar ages for 24 widespread marker tephras erupted since 30,000 calendar (cal.) years ago in New Zealand to help facilitate their use as chronostratigraphic dating tools for the NZ-CES and for other palaeoenvironmental and geological applications. The selected tephras comprise 12 rhyolitic tephras from Taupo, nine rhyolitic tephras from Okataina, one peralkaline rhyolitic tephra from Tuhua, and one andesitic tephra each from Tongariro and Egmont/Taranaki volcanic centres. Age models for the tephras were obtained using three methods: (i) C-based wiggle-match dating of wood from trees killed by volcanic eruptions (these dates published previously); (ii) flexible depositional modelling of a high-resolution C-dated age-depth sequence at Kaipo bog using two Bayesian-based modelling programs, Bacon and OxCal's P_Sequence function, and the IntCal09 data set (with SH offset correction-44±17yr); and (iii) calibration of C ages using OxCal's Tau_Boundary function and the SHCal04 and IntCal09 data sets. Our preferred dates or calibrated ages for the 24 tephras are as follows (youngest to oldest, all mid-point or mean ages of 95% probability ranges): Kaharoa AD 1314±12; Taupo (Unit Y) AD 232±10; Mapara (Unit X) 2059±118cal.yrBP; Whakaipo (Unit V) 2800±60cal.yrBP; Waimihia (Unit S) 3401±108cal.yrBP; Stent (Unit Q) 4322±112cal.yrBP; Unit K 5111±210cal.yrBP; Whakatane 5526±145cal.yrBP; Tuhua 6577±547cal.yrBP; Mamaku 7940±257cal.yrBP; Rotoma 9423±120cal.yrBP; Opepe (Unit E) 9991±160cal.yrBP; Poronui (Unit C) 11,170±115cal.yrBP; Karapiti (Unit B) 11,460±172cal.yrBP; Okupata 11,767±192cal.yrBP; Konini (bed b) 11,880±183cal.yrBP; Waiohau 14,009±155cal.yrBP; Rotorua 15,635±412cal.yrBP; Rerewhakaaitu 17,496±462cal.yrBP; Okareka 21,858±290cal.yrBP; Te Rere 25,171±964cal.yrBP; Kawakawa/Oruanui 25,358±162cal.yrBP; Poihipi 28,446±670cal.yrBP; and Okaia 28,621±1428cal.yrBP.Secondly, we have re-dated the start and end of the Lateglacial cool episode (climate event NZce-3 in theNZ-CES), previously referred to as the Lateglacial climate reversal, as defined at Kaipo bog in eastern North Island, New Zealand, using both Bacon and OxCal P_Sequence modelling with the IntCal09 data set. The ca1200-yr-long cool episode, indicated by a lithostratigraphic change in the Kaipo peat sequence to grey mudwith lowered carbon content, and a high-resolution pollen-derived cooling signal, began 13,739±125cal.yrBP and ended 12,550±140cal.yrBP (mid-point ages of the 95% highest posterior density regions, Bacon modelling). The OxCal modelling, generating almost identical ages, confirmed these ages. The Lateglacial cool episode (ca 13.8-12.6cal.kaBP) thus overlaps a large part of the entire Antarctic Cold Reversal chronozone (ca 14.1-12.4cal.kaBP or ca 14.6-12.8cal.kaBP), and an early part of the Greenland Stadial-1 (Younger Dryas) chronozone (ca 12.9-11.7cal.kaBP). The timing of the Lateglacial cool episode at Kaipo is broadly consistent with the latitudinal patterns in the Antarctic Cold Reversal signal suggested for the New Zealand archipelago from marine and terrestrial records, and with records from southern South America. © 2012 Elsevier Ltd.

A composite pollen-based stratotype for inter-regional evaluation of climatic events in New Zealand over the past 30,000 years (NZ-INTIMATE project)

Our review of paleoclimate information for New Zealand pertaining to the past 30,000 years has identified a general sequence of climatic events, spanning the onset of cold conditions marking the final phase of the Last Glaciation, through to the emergence to full interglacial conditions in the early Holocene. In order to facilitate more detailed assessments of climate variability and any leads or lags in the timing of climate changes across the region, a composite stratotype is proposed for New Zealand. The stratotype is based on terrestrial stratigraphic records and is intended to provide a standard reference for the intercomparison and evaluation of climate proxy records. We nominate a specific stratigraphic type record for each climatic event, using either natural exposure or drill core stratigraphic sections. Type records were selected on thebasis of having very good numerical age control and a clear proxy record. In all cases the main proxy of the type record is subfossil pollen. The type record for the period from ca 30 to ca 18 calendar kiloyears BP (cal. ka BP) is designated in lake-bed sediments from a small morainic kettle lake (Galway tarn) in western South Island. The Galway tarn type record spans a period of full glacial conditions (Last Glacial Coldest Period, LGCP) within the Otira Glaciation, and includes three cold stadials separated by two cool interstadials. The type record for the emergence from glacial conditions following the termination of the Last Glaciation (post-Termination amelioration) is in a core of lake sediments from a maar (Pukaki volcanic crater) in Auckland, northern North Island, and spans from ca 18 to 15.64±0.41 cal. ka BP. The type record for the Lateglacial period is an exposure of interbedded peat and mud at montane Kaipo bog, eastern North Island. In this high-resolution type record, an initial mild period was succeeded at 13.74±0.13 cal. ka BP by a cooler period, which after 12.55±0.14 cal. ka BP gave way to a progressive ascent to full interglacial conditions that were achieved by 11.88±0.18 cal. ka BP. Although a type section is not formally designated for the Holocene Interglacial (11.88±0.18 cal. ka BP to the present day), the sedimentary record of Lake Maratoto on the Waikato lowlands, northwestern North Island, is identified as a prospective type section pending the integration and updating of existing stratigraphic and proxy datasets, and age models. The type records are interconnected by one or more dated tephra layers, the ages of which are derived from Bayesian depositional modelling and OxCal-based calibrations using the IntCal09 dataset. Along with the type sections and the Lake Maratoto record, important, well-dated terrestrial reference records are provided for each climate event. Climate proxies from these reference records include pollen flora, stable isotopes from speleothems, beetle and chironomid fauna, and glacier moraines. The regional composite stratotype provides a benchmark against which to compare other records and proxies. Based on the composite stratotype, we provide an updated climate event stratigraphic classification for the New Zealand region. © 2013 Elsevier Ltd.

The VLT-FLAMES Tarantula Survey XI. A census of the hot luminous stars and their feedback in 30 Doradus

Context. The VLT-FLAMES Tarantula Survey has an extensive view of the copious number of massive stars in the 30 Doradus (30 Dor) star forming region of the Large Magellanic Cloud. These stars play a crucial role in our understanding of the stellar feedback in more distant, unresolved star forming regions. Aims. The first comprehensive census of hot luminous stars in 30 Dor is compiled within a 10 arcmin (150 pc) radius of its central cluster, R136. We investigate the stellar content and spectroscopic completeness of the early type stars. Estimates were made for both the integrated ionising luminosity and stellar wind luminosity. These values were used to re-assess the star formation rate (SFR) of the region and determine the ionising photon escape fraction. Methods. Stars were selected photometrically and combined with the latest spectral classifications. Spectral types were estimated for stars lacking spectroscopy and corrections were made for binary systems, where possible. Stellar calibrations were applied to obtain their physical parameters and wind properties. Their integrated properties were then compared to global observations from ultraviolet (UV) to far-infrared (FIR) imaging as well as the population synthesis code, Starburst99. Results. Our census identified 1145 candidate hot luminous stars within 150 pc of R136 of which >700 were considered to be genuine early type stars and contribute to feedback. We assess the survey to be spectroscopically complete to 85% in the outer regions (>5 pc) but only 35% complete in the region of the R136 cluster, giving a total of 500 hot luminous stars in the census which had spectroscopy. Only 31 were found to be Wolf-Rayet (W-R) or Of/WN stars, but their contribution to the integrated ionising luminosity and wind luminosity was ~ 40% and ~ 50%, respectively. Similarly, stars with M > 100 M (mostly H-rich WN stars) also showed high contributions to the global feedback, ~ 25% in both cases. Such massive stars are not accounted for by the current Starburst99 code, which was found to underestimate the integrated ionising luminosity of R136 by a factor ~ 2 and the wind luminosity by a factor ~ 9. The census inferred a SFR for 30 Dor of 0.073 ± 0.04 M yr . This was generally higher than that obtained from some popular SFR calibrations but still showed good consistency with the far-UV luminosity tracer as well as the combined Hα and mid-infrared tracer, but only after correcting for Hα extinction. The global ionising output was also found to exceed that measured from the associated gas and dust, suggesting that ~6 % of the ionising photons escape the region. Conclusions. When studying the most luminous star forming regions, it is essential to include their most massive stars if one is to determine a reliable energy budget. Photon leakage becomes more likely after including their large contributions to the ionising output. If 30 Dor is typical of other massive star forming regions, estimates of the SFR will be underpredicted if this escape fraction is not accounted for.