Time Scale Of Exchange Research Articles

Spatial and seasonal variability of the air‐sea equilibration timescale of carbon dioxide

AbstractThe exchange of carbon dioxide between the ocean and the atmosphere tends to bring waters within the mixed layer toward equilibrium by reducing the partial pressure gradient across the air‐water interface. However, the equilibration process is not instantaneous; in general, there is a lag between forcing and response. The timescale of air‐sea equilibration depends on several factors involving the depth of the mixed layer, wind speed, and carbonate chemistry. We use a suite of observational data sets to generate climatological and seasonal composite maps of the air‐sea equilibration timescale. The relaxation timescale exhibits considerable spatial and seasonal variations that are largely set by changes in mixed layer depth and wind speed. The net effect is dominated by the mixed layer depth; the gas exchange velocity and carbonate chemistry parameters only provide partial compensation. Broadly speaking, the adjustment timescale tends to increase with latitude. We compare the observationally derived air‐sea gas exchange timescale with a model‐derived surface residence time and a data‐derived horizontal transport timescale, which allows us to define two nondimensional metrics of equilibration efficiency. These parameters highlight the tropics, subtropics, and northern North Atlantic as regions of inefficient air‐sea equilibration where carbon anomalies are relatively likely to persist. The efficiency parameters presented here can serve as simple tools for understanding the large‐scale persistence of air‐sea disequilibrium of CO2 in both observations and models.

Photoinduced mixed valency in zinc porphyrin dimer of triruthenium cluster dyads.

The preparation, electrochemistry, and spectroscopic characterization of three new species, (ZnTPPpy)Ru3O(OAc)6(CO)-pz-Ru3O(OAc)6(CO)L, where ZnTPPpy = zinc(II) 5-(4-pyridyl)-10,15,20-triphenylporphyin, L = pyridyl ligand, and pz = pyrazine, are reported. These porphyrin-coordinated Ru3O–BL–Ru3O (BL = bridging ligand) dyads are capable of undergoing intramolecular electron transfer from the photoexcited Zn porphyrin to Ru3O donor–bridge–acceptor dimer systems. Seven reversible redox processes are observed in the cyclic voltammograms of the newly synthesized dyads, showing no significant electrochemical interaction between the redox active porphyrin and the pyrazine-bridged ruthenium dimer of Ru3O trimers. From the electrochemical behavior of the dyads, large comproportionation constants (Kc = 6.0 × 10(7) for L = dmap) were calculated from the reduction potentials of the Ru(III)Ru(III)Ru(II) clusters, indicating a stable mixed-valence state. Electronic absorption spectra of the singly reduced mixed-valence species show two intervalence charge transfer (IVCT) bands assigned within the Brunschwig–Creutz–Sutin semiclassical three-state model as metal-to-bridge and metal-to-metal in character. The progression from most to least delocalized mixed-valence dimer ions, as determined by the divergence of the IVCT bands and in agreement with electrochemical data, follows the order of L = 4-dimethylaminopyridine (dmap) > pyridine (py) > 4-cyanopyridine (cpy). These systems show dynamic coalescence of the infrared spectra in the ν(CO) region of the singly reduced state. This sets the time scale of electron exchange at <10 ps. The electron transfer from the S1 excited state of the coordinated porphyrin to the dimer is predicted to be thermodynamically favorable, with ΔGFET(0) ranging from −0.54 eV for L = dmap to −0.62 eV for L = cpy. Observation of IVCT band growth under continual photolysis (λexc = 568 nm) confirms a phototriggered intramolecular electron transfer process resulting in a strongly coupled singly reduced mixed-valence species.

Wind-driven circulation patterns in a shallow estuarine lake: St Lucia, South Africa

The spatiotemporal structure of wind-driven circulation patterns and associated water exchanges or residence times can drive important bio-hydrodynamic interactions in shallow lakes and estuaries. The St Lucia estuarine lake in South Africa is an example of such a system. It is a UNESCO World Heritage Site and RAMSAR wetland of international importance but no detailed research on its circulation patterns has previously been undertaken. In this study, a hydrodynamic model was used to investigate the structure of these circulations to provide insights into their role in transport and water exchange processes. A strong diurnal temporal pattern of wind speeds, together with directional switching between two dominant directions, drives intermittent water exchanges and mixing between the lake basins. “High speed flows in shallow nearshore areas with slower upwind counter-flows in deeper areas, linked by circulatory gyres, are key features of the circulation”. These patterns are strongly influenced by the complex geometry of St Lucia and constrictions in the system. Water exchange time scales are non-homogeneous with some basin extremities having relatively long residence times. The influence of the circulation patterns on biological processes is discussed.

Evaluating the uncertainty in exchange parameters determined from off-resonance R1ρ relaxation dispersion for systems in fast exchange

Spin relaxation in the rotating frame (R1ρ) is a powerful NMR technique for characterizing fast microsecond timescale exchange processes directed toward short-lived excited states in biomolecules. At the limit of fast exchange, only kex=k1+k−1 and Φex=pGpE(Δω)2 can be determined from R1ρ data limiting the ability to characterize the structure and energetics of the excited state conformation. Here, we use simulations to examine the uncertainty with which exchange parameters can be determined for two state systems in intermediate-to-fast exchange using off-resonance R1ρ relaxation dispersion. R1ρ data computed by solving the Bloch–McConnell equations reveals small but significant asymmetry with respect to offset (R1ρ (ΔΩ)≠R1ρ (−ΔΩ)), which is a hallmark of slow-to-intermediate exchange, even under conditions of fast exchange for free precession chemical exchange line broadening (kex/Δω>10). A grid search analysis combined with bootstrap and Monte-Carlo based statistical approaches for estimating uncertainty in exchange parameters reveals that both the sign and magnitude of Δω can be determined at a useful level of uncertainty for systems in fast exchange (kex/Δω<10) but that this depends on the uncertainty in the R1ρ data and requires a thorough examination of the multidimensional variation of χ2 as a function of exchange parameters. Results from simulations are complemented by analysis of experimental R1ρ data measured in three nucleic acid systems with exchange processes occurring on the slow (kex/Δω=0.2; pE=∼0.7%), fast (kex/Δω=∼10–16; pE=∼13%) and very fast (kex=39,000s−1) chemical shift timescales.

Controls on the abiotic exchange between aqueous sulfate and water under laboratory conditions

The oxygen atoms in sulfate are known to exchange with water at low pH and at high temperature; however, it is unclear what the timescale for exchange is for the pH and temperature conditions commonly experienced in the laboratory. We present a time series of sulfate‐oxygen isotope data for solutions with two different sulfate concentrations (28 mM and 11 mM), at a range of low to intermediate pH values (1 to 5), using both hydrochloric and acetic acid. Using water enriched in 18O, we show that there is negligible exchange of oxygen atoms between sulfate and water over the course of 390 days. We use the external uncertainty in these results to calculate a lower bound estimate on the timescale for oxygen isotope exchange under these conditions. The lower bound of the timescale for oxygen isotope exchange between sulfate and water at laboratory pH is ~2 × 105 hours (~25 y), which is broadly in agreement with previous estimates. This result validates the use of δ18OSO4 as geochemical tool for a variety of solutions that are subjected to low pH at room temperature.

Long-Distance Water Exchange within Dense Clay Sediments Probed by Two-Time 2H Stimulated Echo NMR Spectroscopy

Two-time correlation functions are measured by deuterium (2H) NMR spectroscopy to probe the long-distance mobility of water molecules strongly confined within dense clay sediments. As checked by 2H NMR multiquantum relaxation measurements, these strongly confined water molecules satisfy the two main requirements for a successful use of that experimental procedure, i.e., slow exchange of the water molecule between its various confining environments and slow modulation of the nuclear couplings responsible for its NMR relaxation. The exchange time scale detected by the attenuation of the two-time 2H NMR stimulated echo is 3 orders of magnitude larger than the average residence time of the water molecules within the interlamellar space of individual clay platelets. Finally, numerical simulations are used to illustrate the impact of local heterogeneities of the clay orientation on the attenuation of the two-time correlation function.

Physical controls and predictability of stream hyporheic flow evaluated with a multiscale model

Improved predictions of hyporheic exchange based on easily measured physical variables are needed to improve assessment of solute transport and reaction processes in watersheds. Here we compare physically based model predictions for an Indiana stream with stream tracer results interpreted using the Transient Storage Model (TSM). We parameterized the physically based, Multiscale Model (MSM) of stream‐groundwater interactions with measured stream planform and discharge, stream velocity, streambed hydraulic conductivity and porosity, and topography of the streambed at distinct spatial scales (i.e., ripple, bar, and reach scales). We predicted hyporheic exchange fluxes and hyporheic residence times using the MSM. A Continuous Time Random Walk (CTRW) model was used to convert the MSM output into predictions of in stream solute transport, which we compared with field observations and TSM parameters obtained by fitting solute transport data. MSM simulations indicated that surface‐subsurface exchange through smaller topographic features such as ripples was much faster than exchange through larger topographic features such as bars. However, hyporheic exchange varies nonlinearly with groundwater discharge owing to interactions between flows induced at different topographic scales. MSM simulations showed that groundwater discharge significantly decreased both the volume of water entering the subsurface and the time it spent in the subsurface. The MSM also characterized longer timescales of exchange than were observed by the tracer‐injection approach. The tracer data, and corresponding TSM fits, were limited by tracer measurement sensitivity and uncertainty in estimates of background tracer concentrations. Our results indicate that rates and patterns of hyporheic exchange are strongly influenced by a continuum of surface‐subsurface hydrologic interactions over a wide range of spatial and temporal scales rather than discrete processes.

Structural and Theoretical Basis for Ligand Exchange on Thiolate Monolayer Protected Gold Nanoclusters

Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering.

Multi-rate distributed fusion estimation for sensor networks with packet losses

This paper presents a distributed fusion estimation method for estimating states of a dynamical process observed by wireless sensor networks (WSNs) with random packet losses. It is assumed that the dynamical process is not changing too rapidly, and a multi-rate scheme by which the sensors estimate states at a faster time scale and exchange information with neighbors at a slower time scale is proposed to reduce communication costs. The estimation is performed by taking into account the random packet losses in two stages. At the first stage, every sensor in the WSN collects measurements from its neighbors to generate a local estimate, then local estimates in the neighbors are further collected at the second stage to form a fused estimate to improve estimation performance and reduce disagreements among local estimates at different sensors. Local optimal linear estimators are designed by using the orthogonal projection principle, and the fusion estimators are designed by using a fusion rule weighted by matrices in the linear minimum variance sense. Simulations of a target tracking system are given to show that the time scale of information exchange among sensors can be slower while still maintaining satisfactory estimation performance by using the developed estimation method.

Expression, purification and preliminary NMR characterization of isotopically labeled wild-type human heterotrimeric G protein αi1

Molecular-level investigation of proteins is increasingly important to researchers trying to understand the mechanisms of signal transmission. Heterotrimeric G proteins control the activation of many critical signal transmission cascades and are also implicated in numerous diseases. As part of a longer-term investigation of intramolecular motions in RGS and Gα proteins in their apo and complexed forms, we have successfully developed a protocol for preparing milligram quantities of highly purified, isotopically labeled wild-type human Gαi1 (hGαi1) subunit for NMR studies. High levels of expression in Escherichia coli can be attributed to the use of the SUMO fusion protein system, a bacterial strain that produces rare codons, supplementation of minimal medium with small quantities of isotopically labeled rich medium and a lowered induction temperature. Purification of hGαi1 utilized affinity and size exclusion chromatography, and protein activity was confirmed using fluorescence-based GTP-binding studies. Preliminary NMR analysis of hGαi1 has shown that high-quality spectra can be obtained at near-physiological temperatures, whereas lower temperature spectra display numerous weak and broadened peaks, providing preliminary evidence for widespread μs-ms timescale exchange. In an effort to further optimize the NMR spectra we prepared a truncated form of hGαi1 (hGαi1-Δ31) in which the 31-residue unstructured N-terminus was removed. This resulted in further improvements in spectral quality by eliminating high-intensity peaks that obscured resonances from structured segments of the protein. We plan to use hGαi1-Δ31 in future investigations of protein dynamics by NMR spectroscopy to gain insight into the role of these motions in RGS/Gα binding selectivity.

Putting a Stop to l,d-Transpeptidases

In this issue of Structure, Lecoq et al. investigated the structural and dynamic basis for the unexpected inhibition of peptidoglycan-crosslinking l,d-transpeptidases by carbapenem antibiotics. In addition to defining a neutral thiol-imidazole catalytic triad, their studies revealed extensive induced motions upon formation of a long-live covalent drug-enzyme complex.

Measurement of the signs of methyl 13C chemical shift differences between interconverting ground and excited protein states by R 1ρ : an application to αB-crystallin

Carr-Purcell-Meiboom-Gill relaxation dispersion (CPMG RD) NMR spectroscopy has emerged as a powerful tool for quantifying the kinetics and thermodynamics of millisecond time-scale exchange processes involving the interconversion between a visible ground state and one or more minor, sparsely populated invisible 'excited' conformational states. Recently it has also become possible to determine atomic resolution structural models of excited states using a wide array of CPMG RD approaches. Analysis of CPMG RD datasets provides the magnitudes of the chemical shift differences between the ground and excited states, Δϖ, but not the sign. In order to obtain detailed structural insights from, for example, excited state chemical shifts and residual dipolar coupling measurements, these signs are required. Here we present an NMR experiment for obtaining signs of (13)C chemical shift differences of (13)CH(3) methyl groups using weak field off-resonance R(1ρ) relaxation measurements. The accuracy of the method is established by using an exchanging system where the invisible, excited state can be converted to the visible, ground state by altering sample conditions so that the signs of Δϖ values obtained from the spin-lock approach can be validated against those measured directly. Further, the spin-lock experiments are compared with the established H(S/M)QC approach for measuring signs of chemical shift differences and the relative strengths of each method are discussed. In the case of the 650 kDa human αB-crystallin complex where there are large transverse relaxation differences between ground and excited state spins the R(1ρ) method is shown to be superior to more 'traditional' experiments for sign determination.

Time and depth scales of fine sediment delivery into gravel stream beds: Constraints from fallout radionuclides on fine sediment residence time and delivery

Particles of fine sediment can clog interstitial pore spaces of coarser grained sediment in river beds and thereby impede the exchange of water, dissolved constituents, and particulate matter with consequent ecological impacts. The extent to which fine sediment reduces connectivity between the stream bed and overlying channel is a function, in part, of sediment residence time. Short residence times imply frequent exchange of matter and reduced impact of fine sediment on stream bed habitat, while long residence times indicate that with respect to fine sediment delivery, the stream bed is more isolated from the overlying channel. Here we present a novel technique to quantify the residence time of river bed sediment at various depths over annual and decadal timescales using the fallout radionuclides (FRNs) 7Be (t1/2=53days) and 210Pbex (t1/2=22.3years). We placed mesh cylinders filled with 7Be-free sediment into a stream bed to quantify the capture of 7Be-tagged particles in the absence of scour and fill. We also took cores to the depth of refusal in alluvial sediment in unregulated and regulated rivers in Vermont and New Hampshire. Sampled watershed areas ranged from 29 to 410km2, and core depths ranged from 19 to 77cm. The 210Pbex activity profiles of cores show that bed sediment is exchanged to the depth of refusal at decadal timescales. In contrast, 7Be activity profiles indicate that fine sediment infiltrating into the bed had residence times ranging from 4 to >300days in unregulated rivers. Cores from a regulated river are notably different—subsurface sediment residence times were always longer than in unregulated rivers at comparable depths, likely owing to restriction of bed mobilization and clogging of bed material by fine sediment. These results suggest that filtration can be an important component of bed material delivery to stream beds, but filtration does not deliver material as deeply into the bed as scour and fill. We find that fallout radionuclides provide direct measurements of time and depth scales of active exchange of particulate matter, which are key controls on hyporheic function.

Using dissolved oxygen concentrations to determine mixed layer depths in the Bellingshausen Sea

Abstract. Concentrations of oxygen (O2) and other dissolved gases in the oceanic mixed layer are often used to calculate air-sea gas exchange fluxes. The mixed layer depth (zmix) may be defined using criteria based on temperature or density differences to a reference depth near the ocean surface. However, temperature criteria fail in regions with strong haloclines such as the Southern Ocean where heat, freshwater and momentum fluxes interact to establish mixed layers. Moreover, the time scales of air-sea exchange differ for gases and heat, so that zmix defined using oxygen may be different than zmix defined using temperature or density. Here, we propose to define an O2-based mixed layer depth, zmix(O2), as the depth where the relative difference between the O2 concentration and a reference value at a depth equivalent to 10 dbar equals 0.5 %. This definition was established by analysis of O2 profiles from the Bellingshausen Sea (west of the Antarctic Peninsula) and corroborated by visual inspection. Comparisons of zmix(O2) with zmix based on potential temperature differences, i.e., zmix(0.2 °C) and zmix(0.5 °C), and potential density differences, i.e., zmix(0.03 kg m−3) and zmix(0.125 kg m−3), showed that zmix(O2) closely follows zmix(0.03 kg m−3). Further comparisons with published zmix climatologies and zmix derived from World Ocean Atlas 2005 data were also performed. To establish zmix for use with biological production estimates in the absence of O2 profiles, we suggest using zmix(0.03 kg m−3), which is also the basis for the climatology by de Boyer Montégut et al. (2004).

Increasing the Exchange Time-Scale That Can Be Probed by CPMG Relaxation Dispersion NMR

Carr-Purcell-Meiboom-Gill relaxation dispersion NMR spectroscopy has emerged as a valuable tool to characterize conformational exchange between major and minor states in a large variety of biomolecules. The window of exchange that is amenable for study, corresponding to rates on the order of 2000 s(-1) or less, is limiting, however. Here we show that a combined analysis of both amide (15)N and (1)H(N) CPMG profiles and major state exchange induced (15)N chemical shift changes leads to significant increases in the exchange time scale for which accurate exchange parameters and chemical shift differences between the interconverting states can be obtained. The utility of the approach is illustrated with examples involving a pair of protein systems that are in the moderately fast exchange regime. In these cases the analysis of dispersion profiles alone is not sufficient to obtain robust measures of exchange parameters and chemical shift differences. Inclusion of major state exchange induced (15)N chemical shift changes measured in ((15)N-(1)H(N)) HMQC and HSQC data sets in addition to the (15)N and (1)H(N) dispersion profiles in the analysis "breaks" the correlation in parameters, allowing accurate values to be obtained. The approach is straightforward to implement and makes use of HMQC/HSQC data sets that are recorded as a matter of routine to obtain chemical shifts of the excited state. It promises to increase the range of exchanging systems involving low populated, transiently formed excited states that can be studied by relaxation dispersion NMR.

The S100A10-Annexin A2 Complex Provides a Novel Asymmetric Platform for Membrane Repair

Membrane repair is mediated by multiprotein complexes, such as that formed between the dimeric EF-hand protein S100A10, the calcium- and phospholipid-binding protein annexin A2, the enlargeosome protein AHNAK, and members of the transmembrane ferlin family. Although interactions between these proteins have been shown, little is known about their structural arrangement and mechanisms of formation. In this work, we used a non-covalent complex between S100A10 and the N terminus of annexin A2 (residues 1-15) and a designed hybrid protein (A10A2), where S100A10 is linked in tandem to the N-terminal region of annexin A2, to explore the binding region, stoichiometry, and affinity with a synthetic peptide from the C terminus of AHNAK. Using multiple biophysical methods, we identified a novel asymmetric arrangement between a single AHNAK peptide and the A10A2 dimer. The AHNAK peptide was shown to require the annexin A2 N terminus, indicating that the AHNAK binding site comprises regions on both S100A10 and annexin proteins. NMR spectroscopy was used to show that the AHNAK binding surface comprised residues from helix IV in S100A10 and the C-terminal portion from the annexin A2 peptide. This novel surface maps to the exposed side of helices IV and IV' of the S100 dimeric structure, a region not identified in any previous S100 target protein structures. The results provide the first structural details of the ternary S100A10 protein complex required for membrane repair.

How can subsurface modifications to hydraulic conductivity be designed as stream restoration structures? Analysis of Vaux's conceptual models to enhance hyporheic exchange

Despite the growing interest in hyporheic exchange and the associated stream ecosystem processes, few studies consider restoration of hyporheic exchange as a design goal. Here we study the design of three types of subsurface structures for hyporheic restoration after conceptual designs published over 40 years ago. Vaux's designs involve modifying the subsurface with low or high hydraulic conductivity material placed at the streambed or adjacent to a confining layer below the stream. In this preliminary analysis of subsurface structure design we use two‐dimensional groundwater flow modeling of structures to simulate structure performance in plane bed streams for ranges of structure geometric design and hydraulic conductivities. Structure performance is evaluated on the basis of total streambed flux, physical extent of hyporheic flow paths created, and residence time distributions along flow paths modified by the structures. High hydraulic conductivity structures bend flow paths toward and through the structures themselves; performance is controlled by the structure hydraulic conductivity. Results show low hydraulic conductivity structure performance is insensitive to the structure material; hyporheic exchange is created by deflecting flow paths away from the structure itself. Time scales of simulated exchange are great enough to promote nitrification, denitrification, respiration, and thermal buffering in the subsurface, though these processes will also be controlled by site‐specific chemical and biological factors. General design recommendations for specific restoration objectives are presented. Results of this study can be extrapolated to further understand the interaction of natural subsurface heterogeneities (e.g., clay and gravel deposits and bedrock knickpoints) and flow fields in creating hyporheic flow paths.

Quantifying millisecond time-scale exchange in proteins by CPMG relaxation dispersion NMR spectroscopy of side-chain carbonyl groups

A new pulse sequence is presented for the measurement of relaxation dispersion profiles quantifying millisecond time-scale exchange dynamics of side-chain carbonyl groups in uniformly (13)C labeled proteins. The methodology has been tested using the 87-residue colicin E7 immunity protein, Im7, which is known to fold via a partially structured low populated intermediate that interconverts with the folded, ground state on the millisecond time-scale. Comparison of exchange parameters extracted for this folding 'reaction' using the present methodology with those obtained from more 'traditional' (15)N and backbone carbonyl probes establishes the utility of the approach. The extracted excited state side-chain carbonyl chemical shifts indicate that the Asx/Glx side-chains are predominantly unstructured in the Im7 folding intermediate. However, several crucial salt-bridges that exist in the native structure appear to be already formed in the excited state, either in part or in full. This information, in concert with that obtained from existing backbone and side-chain methyl relaxation dispersion experiments, will ultimately facilitate a detailed description of the structure of the Im7 folding intermediate.

A record of Antarctic surface temperature between 25 and 50 m.y. ago

Research Article| May 01, 2011 A record of Antarctic surface temperature between 25 and 50 m.y. ago Luigi Dallai; Luigi Dallai * 1CNR (Consiglio Nazionale delle Ricerche), Istituto di Geoscienze e Georisorse, Via Moruzzi 1, 56124, Pisa, Italy *E-mail: dallai@igg.cnr.it. Search for other works by this author on: GSW Google Scholar Ray Burgess Ray Burgess 2School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester M13 9PL, UK Search for other works by this author on: GSW Google Scholar Geology (2011) 39 (5): 423–426. https://doi.org/10.1130/G31569.1 Article history received: 14 Jul 2010 rev-recd: 01 Dec 2010 accepted: 05 Dec 2010 first online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Luigi Dallai, Ray Burgess; A record of Antarctic surface temperature between 25 and 50 m.y. ago. Geology 2011;; 39 (5): 423–426. doi: https://doi.org/10.1130/G31569.1 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyGeology Search Advanced Search Abstract We present the first Antarctic terrestrial record of climate variations through the Cenozoic, based on the hydrogen isotope composition of hydrothermally altered minerals of intrusive rocks. This new record provides an independent geochemical proxy for continental climatic conditions; whereas, most land surface temperature proxies are biological. The temperature record is consistent with the range predicted by global climate models and proxy records for glacial and pre-glacial conditions in the Ross Sea region of Antarctica. The combined stable isotope (O and H) and age (40Ar-39Ar) determinations of hydrous mineral from Cenozoic igneous plutons and dikes show that the protracted time scale of magmatic activity and extensive hydrothermal exchange with local meteoric waters has preserved a semiquantitative climate signal of intervals in which atmospheric temperatures significantly fluctuated. These data also reveal that glacial episodes comparable with current polar conditions occurred repeatedly prior to geographical and thermal isolation of the Antarctic continent. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

Abstract 2328: 15N-backbone and side-chain dynamics of the mutant calcium-binding protein S100B D63N

Abstract Similar to calmodulin and other EF-hand-containing proteins, S100 proteins have no inherent enzymatic activity and perform their biological functions via calcium-dependent protein-protein interactions. Elevated protein levels of S100B have been linked to various types of cancers, including malignant melanomas, glioblastomas, and anaplastic astrocytomas. In the case of malignant melanomas, S100B contributes to cell proliferation by binding to p53 and inhibiting its tumor suppressing properties. However, one property of S100 proteins, including S100B, is that it only binds to calcium tightly when its target protein is bound, a feature that drug design studies for restoring p53 in melanoma must mimic. Therefore, the purpose of this study is to determine the mechanism for how target protein binding to S100B causes an increase in calcium-binding affinity. Previous studies suggest that the increase in calcium affinity in the presence of target is not the result of a structural modification. As an alternative explanation, the mechanism behind this event may involve a reduction in the ligand dynamics coordinating calcium in the canonical EF-hand when target peptide is present. To test this hypothesis with S100B, an asparagine mutant was made in order to have an 15N-probe in the tight-binding EF-hand of S100B for NMR side-chain dynamics with and without target peptide. 15N backbone dynamic experiments (T1, T2, and hetNOE) were collected for the S100B D63N mutant (+/- TRTK-12) at two magnetic fields to determine the effects of peptide binding at multiple time scales. Relaxation dispersion experiments were also collected for backbone and side-chain amides of S100B in the presence and absence of TRTK-12. For the backbone dynamic experiments, motion was detected in the hinge region and C-terminus of helix-4 at multiple timescales in the absence of TRTK-12 (ns-sec timescale). A similar profile was observed for those backbone residues undergoing motion in the chemical exchange time scale seen with the relaxation dispersion data. However, when a molecular target was introduced, the majority of these backbone amides that make up the hydrophobic pocket displayed a general decrease in dynamics. Side chain dynamics in the EF-hand was appreciated in the absence of TRTK-12 peptide, however when the target was present, no chemical exchange was seen with the 15N-D63N probe in the EF-hand. These findings imply that In the presence of target peptide, S100 proteins undergo a decrease in protein dynamics that translates from the site of target binding to the EF-hand. Citation Format: {Authors}. {Abstract title} [abstract]. In: Proceedings of the 102nd Annual Meeting of the American Association for Cancer Research; 2011 Apr 2-6; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2011;71(8 Suppl):Abstract nr 2328. doi:10.1158/1538-7445.AM2011-2328