Leveraging parameter dependencies in high-field asymmetric waveform ion-mobility spectrometry and size exclusion chromatography for proteome-wide cross-linking mass spectrometry

[Image: see text] Ion-mobility spectrometry shows great promise to tackle analytically challenging research questions by adding another separation dimension to liquid chromatography–mass spectrometry. The understanding of how analyte properties influence ion mobility has increased through recent studies, but no clear rationale for the design of customized experimental settings has emerged. Here, we leverage machine learning to deepen our understanding of field asymmetric waveform ion-mobility spectrometry for the analysis of cross-linked peptides. Knowing that predominantly m/z and then the size and charge state of an analyte influence the separation, we found ideal compensation voltages correlating with the size exclusion chromatography fraction number. The effect of this relationship on the analytical depth can be substantial as exploiting it allowed us to almost double unique residue pair detections in a proteome-wide cross-linking experiment. Other applications involving liquid- and gas-phase separation may also benefit from considering such parameter dependencies

The onset of solar cycle 24: What global acoustic modes are telling us

We study the response of the low-degree, solar p-mode frequencies to the unusually extended minimum of solar surface activity since 2007. A total of 4768 days of observations collected by the space-based, Sun-as-a-star helioseismic GOLF instrument are analyzed. A multi-step iterative maximum-likelihood fitting method is applied to subseries of 365 days and 91.25 days to extract the p-mode parameters. Temporal variations of the l=0, 1, and 2 p-mode frequencies are then obtained from April 1996 to May 2009. While the p-mode frequency shifts are closely correlated with solar surface activity proxies during the past solar cycles, the frequency shifts of the l=0 and l=2 modes show an increase from the second half of 2007, when no significant surface activity is observable. On the other hand, the l=1 modes follow the general decreasing trend of the solar surface activity. The different behaviours between the l=0 and l=2 modes and the l=1 modes can be interpreted as different geometrical responses to the spatial distribution of the solar magnetic field beneath the surface of the Sun. The analysis of the low-degree, solar p-mode frequency shifts indicates that the solar activity cycle 24 started late 2007, despite the absence of activity on the solar surface.Comment: To be accepted by A&A (with minor revisions), 4 pages, 3 figures, 1 tabl

Decadal-centennial scale monsoon variations in the Arabian Sea during the Early Holocene

An essential prerequisite for the prediction of future climate change due to anthropogenic input is an understanding of the natural processes that control Earth's climate on timescales comparable to human-lifespan. The Early Holocene period was chosen to study the natural climate variability in a warm interval when solar insolation was at its maximum. The monsoonal system of the Tropics is highly sensitive to seasonal variations in solar insolation, and consequently marine sediments from the region are a potential monitor of past climate change. Here we show that during the Early Holocene period rapid

Living on borrowed time – Amazonian trees use decade‐old storage carbon to survive for months after complete stem girdling

Nonstructural carbon (NSC) reserves act as buffers to sustain tree activity during periods when carbon (C) assimilation does not meet C demand, but little is known about their age and accessibility; we designed a controlled girdling experiment in the Amazon to study tree survival on NSC reserves. We used bomb-radiocarbon (14C) to monitor the time elapsed between C fixation and release (‘age’ of substrates). We simultaneously monitored how the mobilization of reserve C affected δ13CO2. Six ungirdled control trees relied almost exclusively on recent assimilates throughout the 17 months of measurement. The Δ14C of CO2 emitted from the six girdled stems increased significantly over time after girdling, indicating substantial remobilization of storage NSC fixed up to 13–14 yr previously. This remobilization was not accompanied by a consistent change in observed δ13CO2. These trees have access to storage pools integrating C accumulated over more than a decade. Remobilization follows a very clear reverse chronological mobilization with younger reserve pools being mobilized first. The lack of a shift in the δ13CO2 might indicate a constant contribution of starch hydrolysis to the soluble sugar pool even outside pronounced stress periods (regular mixing). © 2018 The Authors. New Phytologist © 2018 New Phytologist Trus

Stratigraphy and chronology of a 15ka sequence of multi-sourced silicic tephras in a montane peat bog, eastern North Island, New Zealand.

We document the stratigraphy, composition, and chronology of a succession of 16 distal, silicic tephra layers interbedded with lateglacial and Holocene peats and muds up to c. 15 000 radiocarbon years (c. 18 000 calendar years) old at a montane site (Kaipo Bog) in eastern North Island, New Zealand. Aged from 665 +/- 15 to 14 700 +/- 95 14C yr BP, the tephras are derived from six volcanic centres in North Island, three of which are rhyolitic (Okataina, Taupo, Maroa), one peralkaline (Tuhua), and two andesitic (Tongariro, Egmont). Correlations are based on multiple criteria: field properties and stratigraphic interrelationships, ferromagnesian silicate mineral assemblages, glass-shard major element composition (from electron microprobe analysis), and radiocarbon dating. We extend the known distribution of tephras in eastern North Island and provide compositional data that add to their potential usefulness as isochronous markers. The chronostratigraphic framework established for the Kaipo sequence, based on both site-specific and independently derived tephra-based radiocarbon ages, provides the basis for fine-resolution paleoenvironmental studies at a climatically sensitive terrestrial site from the mid latitudes of the Southern Hemisphere. Tephras identified as especially useful paleoenvironmental markers include Rerewhakaaitu and Waiohau (lateglacial), Konini (lateglacial-early Holocene), Tuhua (middle Holocene), and Taupo and Kaharoa (late Holocene)

A 1400-Year Oxygen Isotope History from the Ross Sea Area, Antarctica

Four ice cores from the Ross Sea drainage, Antarctica, show patterns of δ18O variations on a time scale of decades to centuries over the last 1400 years without change in the long-term average δ18O. Century scale δ18O fluctuations in the two cores drilled in the Ross Ice Shelf at Station J-9 (82° 23\u27 S, 168° 38\u27 W, elevation 60 m) are highly correlated (P \u3c 2 x 10-4). The long isotope record (\u3e30 000 a) of the 1978 1-9 core thus represents local conditions over at least 102 m and on time scales of 100 years and longer. Regional correlations between the 1-9 δ18O records and those from Ridge BC (82 ° 54\u27S, 136 ° 40\u27W, elevation 509 m) and the Dominion Range (85 ° 15\u27 S, 166 ° 10\u27 E, elevation 2700 m) are barely significant (P ≈ 0.05 for J-9 \u2776 and Dominion Range, δ18O to 1400 years ago) or absent. The failure to find clear regional isotope trends related to climate fluctuations may reflect the finding that between 1957 and 1982 the area was in the transition zone between areas with opposite temperature trends, and showed little or no temperature change. The fact that the records nevertheless show significant δ18O fluctuations highlights the need to base regional climate reconstructions on a regional suite of ice-core records

Low reservoir ages for the surface ocean from mid-Holocene Florida corals

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 23 (2008): PA2209, doi:10.1029/2007PA001527.The 14C reservoir age of the surface ocean was determined for two Holocene periods (4908–4955 and 3008–3066 calendar (cal) B.P.) using U/Th-dated corals from Biscayne National Park, Florida, United States. We found that the average reservoir ages for these two time periods (294 ± 33 and 291 ± 27 years, respectively) were lower than the average value between A.D. 1600 and 1900 (390 ± 60 years) from corals. It appears that the surface ocean was closer to isotopic equilibrium with CO2 in the atmosphere during these two time periods than it was during recent times. Seasonal δ 18O measurements from the younger coral are similar to modern values, suggesting that mixing with open ocean waters was indeed occurring during this coral's lifetime. Likely explanations for the lower reservoir age include increased stratification of the surface ocean or increased Δ14C values of subsurface waters that mix into the surface. Our results imply that a more correct reservoir age correction for radiocarbon measurements of marine samples in this location from the time periods ∼3040 and ∼4930 cal years B.P. is ∼292 ± 30 years, less than the canonical value of 404 ± 20 years.NSF Chemical Oceanography program provided monetary support under grants OCE-9711326, OCE-0137207, and OCE-0551940 (to ERMD)

In vivo protection against NMDA-induced neurodegeneration by MK-801 and nimodipine:Combined therapy and temporal course of protection

Neuroprotection against excitotoxicity by a combined therapy with the N-methyl-D-aspartate (NMDA) receptor antagonist MK-801 and the L-type Ca2+ channel blocker nimodipine was examined using an in vivo rat model of NMDA-induced neurodegeneration. Attention was focused on the neuroprotective potential of this combined drug treatment before and after NMDA-exposure. NMDA was unilaterally injected in the magnocellular nucleus basalis (MEN). Neuronal damage was assessed 12 days after the NMDA-injection by measuring the reduction of cholinergic cortical fibres that originate from the MBN neurons. In controls that received no drug treatment, NMDA-exposure damaged MBN neurons such that 66% of the cholinergic terminals were lost in the ipsilateral parietal cortex. Pretreatment with a nimodipine diet (860 ppm) combined with application of MK-801 (5 mg/kg i.p.) before NMDA-exposure reduced fibre loss by 89% thereby providing a near complete neuroprotection. Combined therapy of MK-801 (5 mg/kg i.p.) and nimodipine (15 mg/kg i.p.) 8 min after NMDA-infusion reduced neuronal injury by 82%, while the same combination given 2 h after the excitotoxic treatment still yielded a 66% protection against neurotoxic damage invoked by NMDA. In conclusion, the present data show that a dual blockade of NMDA-channels and voltage-dependent calcium channels (VDCC's) up to 2 h after NMDA-exposure is able to provide a significant protection against NMDA-neurotoxicity. (C) 1996 Academic Press Limited