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  • American Geophysical Union  (441)
  • Wiley-Blackwell  (255)
  • American Meteorological Society (AMS)
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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Water Resources Research 47 (2011): W00J10, doi:10.1029/2010WR009896.
    Description: Transient storage (TS) zones are important areas of dissolved inorganic nitrogen (DIN) processing in rivers. We assessed sensitivities regarding the relative impact that the main channel (MC), surface TS (STS), and hyporheic TS (HTS) have on network denitrification using a model applied to the Ipswich River in Massachusetts, United States. STS and HTS connectivity and size were parameterized using the results of in situ solute tracer studies in first- through fifth-order reaches. DIN removal was simulated in all compartments for every river grid cell using reactivity derived from Lotic Intersite Nitrogen Experiment (LINX2) studies, hydraulic characteristics, and simulated discharge. Model results suggest that although MC-to-STS connectivity is greater than MC-to-HTS connectivity at the reach scale, at basin scales, there is a high probability of water entering the HTS at some point along its flow path through the river network. Assuming our best empirical estimates of hydraulic parameters and reactivity, the MC, HTS, and STS removed approximately 38%, 21%, and 14% of total DIN inputs during a typical base flow period, respectively. There is considerable uncertainty in many of the parameters, particularly the estimates of reaction rates in the different compartments. Using sensitivity analyses, we found that the size of TS is more important for DIN removal processes than its connectivity with the MC when reactivity is low to moderate, whereas TS connectivity is more important when reaction rates are rapid. Our work suggests a network perspective is needed to understand how connectivity, residence times, and reactivity interact to influence DIN processing in hierarchical river systems.
    Description: This work was supported by the National Science Foundation through DEB- 0614282, BCS-0709685 and the Plum Island Long Term Ecological Research site (NSF OCE-0423565).
    Keywords: Biogeochemistry ; Denitrification ; Hydraulics ; Modeling ; River network ; Transient storage
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 32(12), (2019): 1738-1758, doi:10.1029/2018GB005994.
    Description: Sinking particles strongly regulate the distribution of reactive chemical substances in the ocean, including particulate organic carbon and other elements (e.g., P, Cd, Mn, Cu, Co, Fe, Al, and 232Th). Yet, the sinking fluxes of trace elements have not been well described in the global ocean. The U.S. GEOTRACES campaign in the North Atlantic (GA03) offers the first data set in which the sinking flux of carbon and trace elements can be derived using four different radionuclide pairs (238U:234Th ;210Pb:210Po; 228Ra:228Th; and 234U:230Th) at stations co‐located with sediment trap fluxes for comparison. Particulate organic carbon, particulate P, and particulate Cd fluxes all decrease sharply with depth below the euphotic zone. Particulate Mn, Cu, and Co flux profiles display mixed behavior, some cases reflecting biotic remineralization, and other cases showing increased flux with depth. The latter may be related to either lateral input of lithogenic material or increased scavenging onto particles. Lastly, particulate Fe fluxes resemble fluxes of Al and 232Th, which all have increasing flux with depth, indicating a dominance of lithogenic flux at depth by resuspended sediment transported laterally to the study site. In comparing flux estimates derived using different isotope pairs, differences result from different timescales of integration and particle size fractionation effects. The range in flux estimates produced by different methods provides a robust constraint on the true removal fluxes, taking into consideration the independent uncertainties associated with each method. These estimates will be valuable targets for biogeochemical modeling and may also offer insight into particle sinking processes.
    Description: This study grew out of a synthesis workshop at the Lamont‐Doherty Earth Observatory of Columbia University in August 2016. This workshop was sponsored by the U.S. GEOTRACES Project Office (NSF 1536294) and the Ocean Carbon and Biogeochemistry (OCP) Project Office (NSF 1558412 and NASA NNX17AB17G). The U.S. National Science Foundation supported all of the analytical work on GA03. Kuanbo Zhou measured 228Th in the large size class particles (NSF 0925158 to WHOI). NSF 1061128 to Stony Brook University supported the BaRFlux project, for which Chistina Heilbrun is acknowledged for laboratory and field work. The lead author acknowledges support from a start‐up grant from the University of Southern Mississippi. Two anonymous reviewers are thanked for their constructive comments. All GEOTRACES GA03 data used in this study are accessible through the Biological and Chemical Oceanography Data Management Office (http://data.bco‐dmo.org/jg/dir/BCO/GEOTRACES/NorthAtlanticTransect/), and derived parameters are reported in the supporting information.
    Description: 2019-05-22
    Keywords: Biological carbon pump ; Trace metals ; North Atlantic ; Export ; GEOTRACES
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography and Paleoclimatology 35(12), (2020): e2020PA003962, doi:10.1029/2020PA003962.
    Description: The Great Barrier Reef (GBR) is an internationally recognized and widely studied ecosystem, yet little is known about its sea surface temperature (SST) evolution since the Last Glacial Maximum (LGM) (~20 kyr BP). Here, we present the first paleo‐application of Isopora coral‐derived SST calibrations to a suite of 25 previously published fossil Isopora from the central GBR spanning ~25–11 kyr BP. The resultant multicoral Sr/Ca‐ and δ18O‐derived SST anomaly (SSTA) histories are placed within the context of published relative sea level, reef sequence, and coralgal reef assemblage evolution. Our new calculations indicate SSTs were cooler on average by ~5–5.5°C at Noggin Pass (~17°S) and ~7–8°C at Hydrographer's Passage (~20°S) (Sr/Ca‐derived) during the LGM, in line with previous estimates (Felis et al., 2014, https://doi.org/10.1038/ncomms5102). We focus on contextualizing the Younger Dryas Chronozone (YDC, ~12.9–11.7 kyr BP), whose Southern Hemisphere expression, in particular in Australia, is elusive and poorly constrained. Our record does not indicate cooling during the YDC with near‐modern temperatures reached during this interval on the GBR, supporting an asymmetric hemispheric presentation of this climate event. Building on a previous study (Felis et al., 2014, https://doi.org10.1038/ncomms5102), these fossil Isopora SSTA data from the GBR provide new insights into the deglacial reef response, with near‐modern warming during the YDC, since the LGM.
    Description: This work was funded by National Science Foundation (NSF) award OCE 13‐56948 to B. K. L, with NSF GRFP support DGE‐11‐44155 to L. D. B., and the Australian Research Council (grant no. DP1094001) and ANZIC IODP. Partial support for B. K. L's work on this project also came from the Vetlesen Foundation via a gift to the Lamont‐Doherty Earth Observatory. T. F. received funding from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—Project number 180346848, through Priority Program 527 “IODP.” A. T. received support from the UK Natural Environment Research Council (NE/H014136/1 and NE/H014268/1). M. T. thanks Ministry of Earth Sciences for support (NCPOR contribution no. J‐84/2020‐21). L. D. B. would also like to thank Kassandra Costa for her input regarding error analysis.
    Description: 2021-06-11
    Keywords: Great Barrier Reef ; coral ; Younger Dryas Chronozone ; sea surface temperature ; Sr/Ca ; Last Glacial Maximum
    Repository Name: Woods Hole Open Access Server
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  • 4
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous studies have demonstrated that His 12 plays a major role in the pH-dependent stability of the helix formed by the isolated C-peptide (residues 1-13 of ribonuclease A). Here, amino acid replacement experiments show that His 12+ stabilizes the C-peptide helix chiefly by interacting with Phe 8. The Phe 8 ⃛ His 12+ ring interaction is specific for the protonated form of His 12 (His 12+) and the interaction is not screened significantly by NaCl, unlike the charged group ⃛ helix dipole interactions studied earlier in C-peptide. Analogs of C-peptide that are unable to form the Phe 8 ⃛ His 12+ interaction show large increases in helix content for Phe → Ala and His → Ala. Therefore, the helical tendencies of the individual residues Phe, His, and Ala are important in determining the result of a replacement experiment. Since the side chains of Phe 8 and His 12 probably interact within the N-terminal helix of ribonuclease A, the existence of the Phe 8 ⃛ His 12+ interaction in the isolated C-peptide helix adds to the evidence that the C-peptide helix is an autonomous folding unit.
    Additional Material: 8 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of two agonist-antagonist pairs of bradykinin (Arg1-Pro2-Pro3-Gly4-Phe5-Ser6-Pro7-Phe8-Arg9) analogues were studied in CD3OH/H2O solution by 1H-nmr techniques. The first agonist peptide studied, D-Arg0-Arg1-Pro2-Hyp3-Gly4-Thi5-Ser6-Pro7-Thi8-Arg9, differs from the bradykinin sequence by the addition of D-Arg0, the replacement of the Phe moieties in positions 5 and 8 by Thi (Thi = β-(2-thienyl)-L-alanine), and Hyp3 (Hyp = L-4-hydroxy-L-proline) in position 3. In the corresponding antagonist sequence, Pro7 is replaced by D-Phe7. The second agonist-antagonist pair studied does not contain the D-Arg0 residue, which is present only to slow down the rate of metabolism. Based on complete resonance assignments from two-dimensional total correlation spectroscopy and rotating frame nuclear Overhauser effect spectroscopy spectra at 500 MHz, the peptides were analyzed in terms of intraresidue, sequential, and medium-range nuclear Overhauser effects, amide proton temperature coefficients, and vicinal coupling constants. Both agonist peptides show clear evidence for the existence of a type I β-turn comprising the C-terminal residues Ser6-Pro7-Thi8-Arg9 in fast conformational equilibrium with extended structures throughout. Although the conformational space is dominated by extended structures, the presence of the β-turn is spectroscopically clearly discernible. The two antagonist peptides, on the other hand, do not show evidence of turn formation but rather the presence of an extended conformation with some irregularities in the N-terminal region of the peptide. While the existence of a turn at the C-terminal end of bradykinin and its analogues with agonist activity has been predicted by empirical calculations and measurements in very apolar solvents, this study, for the first time, provides evidence based on physical data in a polar solvent environment that the turn is present, that it is type I and that it is essential for agonist activity. In the particular solvent used in these studies, the Pro7 to D-Phe7 substitution precluded the formation of the turn for the C-terminal residues of the antagonist. © 1993 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 33 (1993), S. 1237-1247 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bradykinin (BK) is a peptide hormone with sequence Arg1-Pro2-Pro3-Gly4-Phe5-Ser6-Pro7-Phe8-Arg9 and has been implicated in a multitude of pathophysiological processes such as the ability to lower systemic blood pressure and stimulate pain. BK analogues having bulky, β-branched D-aliphatic residues at position 7 combined with bulky L-aliphatic residues at position 8 have now been observed to be strong antagonists. Conformational studies based on two-dimensional nmr experiments in methanol/water (80/20 v/v) were carried out on several such active antagonists in a polar solvent. Included in this study were the very active antagonists, [D-Arg0, Hyp3, Thi5, D-Cpg7, Cpg8]-BK [Cpg: α-cyclo-pentyl-glycine; Hyp: trans-4-hydroxy-L-proline; Thi: β-(2-thienyl)-L-alanine] (I), [D-Arg0, Hyp3, D-Cpg7, Cpg8] -BK (II), as well as its variant with D-Cpg7 replaced by Cpg7, namely [D-Arg0, Hyp3, Cpg7, Cpg8]-BK (III). A turn-like structure, which coexists with the extended conformation, was observed between residues 2 and 5 for the most active antagonists I and II, in direct correlation with the peptide activities. No turn-like structure was found for residues 6-9. In peptide III, a turn-like structure was not identified. The existence of a turn at the C-terminal end of bradykinin and its analogues has been predicted by empirical calculations and supported by nmr measurements. But the present nmr study on the most active antagonists (I, II) does not support this hypothesis. Instead, the data suggest that a turn-like structure between residues 2 and 5 could be important for antagonist activity. Finally, one weak inhibitor [D-Cpg7]-BK (IV) showed no defined secondary structure. © 1993 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 37 (1995), S. 143-155 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bradykinin (BK) is involved in regulation of every major physiological system and is an initiator or mediator of many pathophysiological conditions. Rapid progress in understanding these aspects of BK biology has come since the discovery of BK antagonists. This article reviews principal points in the history of the kallikrein-kinin field and of kinin biology. The chemistry and development of antagonists for B1 and B2 kinin receptors is discussed. Uses of the antagonists in biomedical research and potential clinical applications are presented. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 8
    ISSN: 0006-3525
    Keywords: bradykinin receptor antagonists ; bradykinin antagonist conformation ; molecular dynamics ; nmr ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Extensive proton magnetic resonance experiments were carried out on three bradykinin peptide antagonists B-9430, B-9436, and B-9858 in aqueous solutions as well as in sodium dodecylsulphate micelles (B-9430 and B-9436) and CD3OH/H2O (60%/40%) mixtures for B-9858. All three peptides showed no observable secondary structure in aqueous solution. However, in their respective structure-inducing solvents, B-9430 (B1 and B2 receptor antagonist) and B-9436 (a B2 receptor antagonist) exhibit a type II β-turn involving residues 2-5, and B-9430 also exhibits a type II′ β-turn involving residues 6-9 (in sodium dodecylsulfate micellar solutions), whereas B-9858, a B1-specific receptor antagonist, exhibits only a type II β-turn involving residues 2-5 (in CD3OH/H2O solutions). Simulated annealing calculations on B-9858 confirm the experimental conclusions based on the nmr data. In addition, simulated annealing of the (2S, 3aS, 7aS)-octahydroindole-2-carboxylic acid (Oic residue), which is present in two of the three decapeptides studied, show that the one-chair conformation of the six-membered ring predominates, in agreement with the experimental data. The activities of these peptides are compared with their secondary structures and the specific receptor activity appears to depend on the presence of specific amino acid residues, such as N-(2-indanyl)glycine (Nig) and D[α-(2-indanyl)glycine] (D-Igl) as well as on elements of secondary structure. © 1997 John Wiley & Sons, Inc. Biopoly 42: 521-535, 1997
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 30 (1986), S. 529-540 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Extensional elastic moduli have been calculated for several organic high polymers based on the modified neglect of diatomic overlap (MNDO) Hamiltonian. Standard semiempirical methods, by application of the Born-von Karman boundary conditions, can be used to calculate heats of formation of polymer chain sections, or computational unit cells, called clusters. Unit cell heats of formation at elongated translation vectors, combined with experimental or estimated densities, allow for the calculation of elastic moduli. Two potential sources of error were identified: (a) finite geometry optimization can result in pseudorandom errors in the calculated heat of formation, and (b) anharmonic distortion can become significant at large strains. Errors due to both causes can typically be minimized if strains between 3 and 10% are selected. As expected, the calculated moduli, although higher than those observed experimentally, agree with longitudinal values for perfectly oriented systems.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 35 (1989), S. 305-313 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that infinite long polyacene chains may have three energetically close but structurally distinct isomers (a symmetrical, sym, form and two lower symmetry forms: one with double bonds in a trans and another isomer with double bonds in a cis pattern). The energetics is based on solid state MNDO theory. We discuss that the symmetrical form has a substantial energy gap Eg in the Hartree-Fock approach owing to exact exchange terms, which are nonlocal. Broken symmetry Hartree-Fock (HF) solutions for polyacene are also described. An angularly distorted structure suggested earlier on Jahn-Teller grounds is found to be energetically not favorable.
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