Ab initio equilibrium constants for H2O–H2O and H2O–CO2

Ab initio 6‐31G** electronic structure calculations have been used to determine the minimum energy geometries and vibrational frequencies of molecular clusters of water and carbon dioxide. Application of statistical thermodynamics leads to theoretical equilibrium constants for gas phase dimerization of water and the formation of an adduct of carbon dioxide with water.The low energy vibrations of the clusters lead to much larger contributions to the vibrational partitioning of the energy than do the fundamental vibrations of the monomeric species. A new ‘‘Harmonic‐Morse’’ formula is derived to estimate anharmonicity from optimized harmonic frequencies and two additional values on the potential surface for each vibration. These ab initiocalculations of equilibrium constants are very close to recent measurements and fall within the range of values obtained by other methods. This no‐parameter treatment gives excellent agreement for the equilibrium of H2O–CO2 near the supercritical fluid range of CO2 and suggests that a ‘‘Theory of Significant Clusters’’ may be extended to a model of supercritical fluids which includes the effects of anharmonicity

THz absorption spectrum of the CO2–H2O complex: Observation and assignment of intermolecular van der Waals vibrations

Terahertz absorption spectra have been recorded for the weakly bound CO2-H2O complex embedded in cryogenic neon matrices at 2.8 K. The three high-frequency van der Waals vibrational transitions associated with out-of-plane wagging, in-plane rocking, and torsional motion of the isotopic H2O subunit have been assigned and provide crucial observables for benchmark theoretical descriptions of this systems' flat intermolecular potential energy surface. A (semi)-empirical value for the zero-point energy of 273 ± 15 cm(-1) from the class of intermolecular van der Waals vibrations is proposed and the combination with high-level quantum chemical calculations provides a value of 726 ± 15 cm(-1) for the dissociation energy D0

Excited State Dynamics of Bistridentate and Trisbidentate RuII Complexes of Quinoline-Pyrazole Ligands

Three homoleptic ruthenium(II) complexes, [Ru(Q3PzH)3]2+, [Ru(Q1Pz)3]2+, and [Ru(DQPz)2]2+, based on the quinoline-pyrazole ligands, Q3PzH (8-(3-pyrazole)-quinoline), Q1Pz (8-(1-pyrazole)-quinoline), and DQPz (bis(quinolinyl)-1,3-pyrazole), have been spectroscopically and theoretically investigated. Spectral component analysis, transient absorption spectroscopy, density functional theory calculations, and ligand exchange reactions with different chlorination agents reveal that the excited state dynamics for Ru(II) complexes with these biheteroaromatic ligands differ significantly from that of traditional polypyridyl complexes. Despite the high energy and low reorganization energy of the excited state, nonradiative decay dominates even at liquid nitrogen temperatures, where triplet metal-to-ligand-charge-transfer emission quantum yields range from 0.7 to 3.8%, and microsecond excited state lifetimes are observed. In contrast to traditional polypyridyl complexes where ligand exchange is facilitated by expansion of the metal-ligand bonds to stabilize a metal-centered state, photoinduced ligand exchange occurs in the bidentate complexes despite no substantial MC state population, while the tridentate complex is extremely photostable despite an activated decay route, highlighting the versatile photochemistry of nonpolypyridine ligands.\ua0\ua9 2019 American Chemical Society

Nano-Imprinted Thin Films of Reactive, Azlactone-Containing Polymers: Combining Methods for the Topographic Patterning of Cell Substrates with Opportunities for Facile Post-Fabrication Chemical Functionalization

Laser scanning confocal microscopy (LSCM) and atomic force microscopy (AFM) were used to characterize changes in nanoscale structure that occur when ultrathin polyelectrolyte multilayers (PEMs) are incubated in aqueous media. The PEMs investigated here were fabricated by the deposition of alternating layers of plasmid DNA and a hydrolytically degradable polyamine onto a precursor film composed of alternating layers of linear poly(ethylene imine) (LPEI) and sodium poly(styrene sulfonate) (SPS). Past studies of these materials in the context of gene delivery revealed transformations from a morphology that is smooth and uniform to one characterized by the formation of nanometer-scale particulate structures. We demonstrate that in-plane registration of LSCM and AFM images acquired from the same locations of films fabricated using fluorescently labeled polyelectrolytes allows the spatial distribution of individual polyelectrolyte species to be determined relative to the locations of topographic features that form during this transformation. Our results suggest that this physical transformation leads to a morphology consisting of a relatively less disturbed portion of film composed of polyamine and DNA juxtaposed over an array of particulate structures composed predominantly of LPEI and SPS. Characterization by scanning electron microscopy and energy-dispersive X-ray microanalysis provides additional support for this interpretation. The combination of these different microscopy techniques provides insight into the structures and dynamics of these multicomponent thin films that cannot be achieved using any one method alone, and could prove useful for the further development of these assemblies as platforms for the surface-mediated delivery of DNA

Ice surface changes during recent glacial cycles along the Jutulstraumen and Penck Trough ice streams in western Dronning Maud Land, East Antarctica

Reconstructing past ice-sheet surface changes is key to testing and improving ice-sheet models. Data constraining the past behaviour of the East Antarctic Ice Sheet are sparse, limiting our understanding of its response to past, present and future climate change. Here, we report the first cosmogenic multi-nuclide (10Be, 26Al, 36Cl) data from bedrock and erratics on nunataks along the Jutulstraumen and Penck Trough ice streams in western Dronning Maud Land, East Antarctica. Spanning elevations between 741 and 2394 m above sea level, the samples have apparent exposure ages between 2 ka and 5 Ma. The highest-elevation bedrock sample indicates (near-) continuous minimum exposure since the Pliocene, with a low apparent erosion rate of 0.15 ± 0.03 m Ma−1, which is similar to results from eastern Dronning Maud Land. In contrast to studies in eastern Dronning Maud Land, however, our data show clear indications of a thicker-than-present ice sheet within the last glacial cycle, with a thinning of ∼35–120 m during the Holocene (∼2–11 ka). Difficulties in separating suitable amounts of quartz from the often quartz-poor rock-types in the area, and cosmogenic nuclides inherited from exposure prior to the last deglaciation, prevented robust thinning estimates from elevational profiles. Nevertheless, the results clearly demonstrate ice-surface fluctuations of several hundred meters between the current grounding line and the edge of the polar plateau for the last glacial cycle, a constraint that should be considered in future ice-sheet model simulations

The Calcitonin and Glucocorticoids Combination: Mechanistic Insights into Their Class-Effect Synergy in Experimental Arthritis

PMCID: PMC3564948This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited

Changes in vertical ice extent along the East Antarctic Ice Sheet margin in western Dronning Maud Land – initial field and modelling results of the MAGIC-DML collaboration

Constraining numerical ice sheet models by comparison with observational data is crucial to address the interactions between cryosphere and climate at a wide range of scales. Such models are tested and refined by comparing model predictions of past ice geometries with field-based reconstructions from geological, geomorphological, and ice core data. However, for the East Antarctic Ice sheet, there is a critical gap in the empirical data necessary to reconstruct changes in ice sheet geometry in the Dronning Maud Land (DML) region. In addition, there is poor control on the regional climate history of the ice sheet margin, because ice-core locations, where detailed reconstructions of climate history exist, are located on high inland domes. This leaves numerical models ofregional glaciation history in this near-coastal area largely unconstrained. MAGIC-DML is an ongoing Swedish-US-Norwegian-German-UK collaboration with a focus on improvingice sheet models of the western DML margin by combining advances in modeling with filling critical data gaps regarding the timing and pattern of ice-surface changes. A combination of geomorphological mapping using remote sensing data, field observations, cosmogenic nuclide surface exposure dating, and numerical ice sheetmodeling are being used in an iterative manner to produce a comprehensive reconstruction of the glacial historyof western DML. Here, we present an overview of the project, field evidence for formerly higher ice surfaces and in-situ cosmogenic nuclide measurements from the 2016/17 expedition. Preliminary field evidence indicate that interior sectors of DML have experienced a general decrease in ice sheet thickness since the late Miocene, with potential episodes of increasing thickness in the late Pleistocene (700-300 ka, 250-75 ka). To aid in interpreting these field data, new high-resolution ice sheet model reconstructions, constraining ice sheet configurations during key episodes, are presented

Physiological responses to low-force work and psychosocial stress in women with chronic trapezius myalgia

<p>Abstract</p> <p>Background</p> <p>Repetitive and stressful work tasks have been linked to the development of pain in the trapezius muscle, although the underlying mechanisms still remain unclear. In earlier studies, it has been hypothesized that chronic muscle pain conditions are associated with imbalance in the autonomic nervous system, predominantly expressed as an increased sympathetic activity. This study investigates whether women with chronic trapezius myalgia show higher muscle activity and increased sympathetic tone at baseline and during repetitive low-force work and psychosocial stress, compared with pain-free controls.</p> <p>Methods</p> <p>Eighteen women with chronic trapezius myalgia (MYA) and 30 healthy female controls (CON) were studied during baseline rest, 100 min of repetitive low-force work, 20 min of psychosocial stress (Trier Social Stress Test, TSST), and 80 min recovery. The subjects rated their pain intensity, stress and energy level every 20 min throughout the experiment. Muscle activity was measured by surface electromyography in the trapezius muscle (EMGtrap) and deltoid muscle (EMGdelt). Autonomic reactivity was measured through heart rate (HR), skin conductance (SCL), blood pressure (MAP) and respiration rate (Resp).</p> <p>Results</p> <p>At baseline, EMGtrap, stress ratings, and HR were higher in MYA than in CON. Energy ratings, EMGdelt, SCL, MAP and Resp were, however, similar in the two groups. Significant main group effects were found for pain intensity, stress ratings and EMGtrap. Deltoid muscle activity and autonomic responses were almost identical in MYA and CON during work, stress and recovery. In MYA only, pain intensity and stress ratings increased towards the end of the repetitive work.</p> <p>Conclusion</p> <p>We found increased muscle activity during uninstructed rest in the painful muscle of a group of women with trapezius myalgia. The present study could not confirm the hypothesis that chronic trapezius myalgia is associated with increased sympathetic activity. The suggestion of autonomic imbalance in patients with chronic local or regional musculoskeletal pain needs to be further investigated.</p

Mid-Pleistocene ice sheet fluctuations from cosmogenic nuclide field constraints in western Dronning Maud Land, Antarctica

The East Antarctic Ice Sheet (EAIS) is generally assumed to have been relatively insensitive to Quaternary climat echange. However, recent studies have shown potential instabilities in coastal, marine sectors of the EAIS. In addition, long-term climate reconstructions and modelling experiments indicate the potential for significant changes in ice volume and ice sheet configuration since the Pliocene. Hence, more empirical evidence for ice surface and ice volume changes is required to discriminate between contrasting inferences. MAGIC-DML is an ongoing Swedish-US-Norwegian-German-UK collaboration focused on improving ice sheetm odels by filling critical data gaps that exist in our knowledge of the timing and pattern of ice surface changes along the western Dronning Maud Land (DML) margin and combining this with advances in numerical techniques. As part of the project, field studies in the 2016/17 and 2017/18 austral summers targeted selected sites spanning accessible altitudes in the Heimefrontfjella, Vestfjella, Ahlmannryggen, Borgmassivet, and Kirwanveggen nunatakranges for in situcosmogenic nuclide sampling. Comparing concentrations of nuclides with widely differing half-lives in bedrock and erratics from a range of altitudes above modern ice surfaces can provide information on ice sheet fluctuations and complex burial and exposure histories, and thus, past configurations of non-erosive ice. Quartz-bearing rock types were sampled and analyzed for 10Be (t1/21.4 My),14C (t1/25.7 ky),26Al (t1/2705ky), and 21Ne (stable), and mafic lithologies for36Cl (t1/2301 ky). Results thus far for 3210Be and 26Al isotope pairs complemented with seven21Ne measurements have yielded some consistent patterns of paleoglaciation for the western DML margin. Eight out of fourteen bedrock samples from high-elevation (1700-2238 m a.s.l.) ridges and summits return some of the oldest exposure ages in Antarctica and have consistent 10Be,26Al, and 21Ne minimum apparent exposure ages of 1.8-4.1 Ma. Initial results therefore indicate that parts of the ice sheet marginal to the Antarctic plateau, along the Heimefrontfjella range, generally have experienced a decrease in ice thickness since the late Miocene. Another six bedrock samples (1556-1732 ma.s.l.) fall in the 300-700 ka range, and they all show significant burial. At face value, perhaps this indicates aregional ice sheet surface above 1700 m a.s.l. for much of the Plio-early Pleistocene. All other samples analyzedto date are erratics from lower elevation and more coastal sites (10 from nunataks at 553-1400 m a.s.l., and 6 froma surface moraine at 1385 m a.s.l.), exhibiting ages between 59 and 275 ka, save for two (4 and 6 ka). Whereas almost all of the nunatak erratics (including the young ones) show significant burial durations, five of the six surface moraine samples do not. These 2016/17 field samples are not yet leading to conclusive age constraints but already start to paint a picture of the western DML margin being relatively stable although there was possibly one or more episodes of relatively limited ice thickening during the last 700 ka