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  • 1
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 22.63 MHz 13C NMR spectra of a series of alkylated thioureas are reported. Characteristic Z and E spectral regions were found for the 13C = S resonances. The two regions were generally found to be non-overlapping for the series, with the region of the Z, Z resonances occurring more downfield than those of either the Z, E or E, Z conformers in the cases of 1,3-disubstitution. The Z, Z configuration became favored and the relative chemical shift difference (Rδ) increased linearly with increasing substituent size. At 217 K, hindered internal rotation caused a multiplicity of resonances which were normally single peaks in the broad band 1H decoupled 62.86 MHz 13C spectrum of CH3NHCSNH(CH2)2NHCSNHCH3 (2MTE) at room temperature. The trends in chemical shifts and populations were employed to assign tentatively the resonances of five of the six possible configurational isomers contributing to the 2MTE spectra at 217 K. The isomer populations are given. The 13C NMR spectra reported here led to signal assignments of Z and E isomers which supported prior 1H NMR results and contradicted more recent results of another 13C NMR study of N-methylthiourea. The major peak of the exchange doublet occurs at relatively high field strengths in both methanol-d5.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependent spectra of several mono-, di- and trialkylthioureas have been recorded. Free energy barriers to internal rotation about the C—N bonds have been calculated. In thioureas that were unsymmetrically substituted, free energy barriers were found to be different for each C—N bond with the more substituted amino group exhibiting the higher barrier. The monosubstituted thioureas showed different rotational barriers for the NH2 groups of the cis and trans isomers, respectively. The free energy barriers for the trans isomers were found to be substituent dependent and substantiate the reassignment of the high and low field substituent signals to the trans and cis isomers, respectively. The spectrum of 1-methyl-3-t-butylthiourea indicates restricted rotation of the t-butyl group at temperatures below 200 K.
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  • 3
    Publication Date: 2022-10-26
    Description: Author Posting. © The Author(s), 2020. This is the author's version of the work. It is posted here by permission of Nature Research for personal use, not for redistribution. The definitive version was published in Bramante, J. F., Ford, M. R., Kench, P. S., Ashton, A. D., Toomey, M. R., Sullivan, R. M., Karnauskas, K. B., Ummenhofer, C. C., & Donnelly, J. P. (2020). Increased typhoon activity in the Pacific deep tropics driven by Little Ice Age circulation changes. Nature Geoscience, 13, 806–811. doi:10.1038/s41561-020-00656-2.
    Description: The instrumental record reveals that tropical cyclone activity is sensitive to oceanic and atmospheric variability on inter-annual and decadal scales. However, our understanding of the influence of climate on tropical cyclone behaviour is restricted by the short historical record and the sparseness of prehistorical reconstructions, particularly in the western North Pacific, where coastal communities suffer loss of life and livelihood from typhoons annually. Here, to explore past regional typhoon dynamics, we reconstruct three millennia of deep tropical North Pacific cyclogenesis. Combined with existing records, our reconstruction demonstrates that low-baseline typhoon activity prior to 1350 ce was followed by an interval of frequent storms during the Little Ice Age. This pattern, concurrent with hydroclimate proxy variability, suggests a centennial-scale link between Pacific hydroclimate and tropical cyclone climatology. An ensemble of global climate models demonstrates a migration of the Pacific Walker circulation and variability in two Pacific climate modes during the Little Ice Age, which probably contributed to enhanced tropical cyclone activity in the tropical western North Pacific. In the next century, projected changes to the Pacific Walker circulation and expansion of the tropics will invert these Little Ice Age hydroclimate trends, potentially reducing typhoon activity in the deep tropical Pacific.
    Description: This work was supported by the Strategic Environmental Research and Development Program (SERDP RC-2336). C.C.U. acknowledges support from NSF under AGS-1602455. We thank student intern D. Carter for extensive labwork on core LTD3. We acknowledge the WCRP’s Working Group on Coupled Modelling, which is responsible for CMIP, and we thank the climate modelling groups for producing and making available their model output. CMIP5 model output was provided by the WHOI CMIP5 Community Storage Server via their website: http://cmip5.whoi.edu/. Any use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the US Government.
    Description: 2021-05-16
    Keywords: Tropical cyclones ; Little Ice Age ; Last millennium ; Paleoclimate
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 4
    Publication Date: 2022-10-21
    Description: The instrumental record reveals that tropical cyclone activity is sensitive to oceanic and atmospheric variability on inter-annual and decadal scales. However, our understanding of climate’s influence on tropical cyclone behavior is restricted by the short historical record and sparse prehistorical reconstructions, particularly in the western North Pacific where coastal communities suffer loss of life and livelihood from typhoons annually. Here we reconstruct three millennia of deep tropical North Pacific cyclogenesis and compare with other records to explore past regional typhoon dynamics. These records demonstrate low baseline activity prior to 1350 C.E. followed by a rapid culmination in activity during the Little Ice Age. This pattern is concurrent with hydroclimate proxy variability, suggesting a centennial-scale link between Pacific hydroclimate and tropical cyclone climatology. Using an ensemble of global climate models, we demonstrate that migration of the Pacific Walker circulation and variability in two Pacific climate modes during the Little Ice Age contributed to enhanced tropical cyclone activity in the tropical western North Pacific. Changes to Walker Circulation and expansion of the tropics projected for the next century invert Little Ice Age hydroclimate trends, potentially reducing typhoon activity in the deep tropical Pacific.
    Description: This project was supported by the Strategic Environmental Research and Development Program through award SERDP RC-2336
    Keywords: Tropical cyclones ; Little Ice Age ; Last millennium ; Paleoclimate
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 5
    Publication Date: 2022-10-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in E. J., Donnelly, J. P., van Hengstum, P. J., Wiman, C., Sullivan, R. M., Winkler, T. S., d'Entremont, N. E., Toomey, M., & Albury, N. Intense hurricane activity over the past 1500 years at South Andros Island, the Bahamas. Paleoceanography and Paleoclimatology, 34(11), (2019): 1761-1783, doi:10.1029/2019PA003665.
    Description: Hurricanes cause substantial loss of life and resources in coastal areas. Unfortunately, historical hurricane records are too short and incomplete to capture hurricane‐climate interactions on multi‐decadal and longer timescales. Coarse‐grained, hurricane‐induced deposits preserved in blue holes in the Caribbean can provide records of past hurricane activity extending back thousands of years. Here we present a high resolution record of intense hurricane events over the past 1500 years from a blue hole on South Andros Island on the Great Bahama Bank. This record is corroborated by shorter reconstructions from cores collected at two nearby blue holes. The record contains coarse‐grained event deposits attributable to known historical hurricane strikes within age uncertainties. Over the past 1500 years, South Andros shows evidence of four active periods of hurricane activity. None of these active intervals occurred in the past 163 years. We suggest that Intertropical Convergence Zone position modulates hurricane activity on the island based on a correlation with Cariaco Basin titanium concentrations. An anomalous gap in activity on South Andros Island in the early 13th century corresponds to a period of increased volcanism. The patterns of hurricane activity reconstructed from South Andros Island closely match those from the northeastern Gulf of Mexico but are anti‐phased with records from New England. We suggest that either changes in local environmental conditions (e.g., SSTs) or a northeastward shift in storm tracks can account for the increased activity in the western North Atlantic when the Gulf of Mexico and southeastern Caribbean are less active.
    Description: This work was funded by the National Science Foundation Graduate Research Fellowship (to E.J.W.), National Science Foundation grant OCE‐1356708 (to J.P.D. and P.J.vH.), the Dalio Explore Foundation and the USGS Land Change Science Program (M.R.T.). We are grateful to members of WHOI Coastal Systems Group, in particular Stephanie Madsen, for their help in the processing core samples. We thank two anonymous reviewers, Matthew Lachniet, Marci Robinson (USGS) and Miriam Jones (USGS) for their helpful feedback on earlier versions of this manuscript. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. The data are available on the National Climatic Data Center (http://www.ncdc.noaa.gov/dataaccess/paleoclimatology‐data) and WHOI Coastal Systems Group (https://web.whoi.edu/coastal‐group/) websites.
    Keywords: Paleohurricanes ; Carbonate tidal flats ; Blue holes ; Andros ; Bahamas
    Repository Name: Woods Hole Open Access Server
    Type: Article
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