Functionalized Adamantane Tectons Used in the Design of Mixed-Ligand Copper(II) 1,2,4-Triazolyl/Carboxylate Metal–Organic Frameworks

Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr2pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H4-adtc) platform for the construction of neutral heteroleptic copper(II) metal−organic frameworks. Two coordination polymers, [{Cu4(OH)2(H2O)2}{Cu4(OH)2}(tr2pr)2(H-adtc)4]·2H2O (1) and [Cu4(OH)2(tr2ad)2(H-adtc)2(H2O)2]·3H2O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N1,N2-1,2,4-triazolyl (tr) and μ3-OH− groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu4(OH)2} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu4(OH)2} secondary building block and trideprotonated carboxylate H-adtc3− can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing μ3- or μ4-binding patterns, introduce additional integrating links between the neighboring {Cu4(OH)2} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J1 = −109 cm−1 and J2 = −21 cm−1), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = −2.5 cm−1).

Distamycin-NA: A DNA Analog with an Aromatic Heterocyclic Polyamide Backbone. Part 1. Synthesis and structural analysis of monomers and dimers containing the nucleobase uracil

The synthesis of the monomeric building block 13 and its constitutional isomer 12 of a new type of DNA analog, distamycin-NA, is presented (Schemes 1 and 2). This building block consists of a uracil base attached to a thiophene core unit via a biaryl-like axis. Next to the biaryl-like axis on the thiophene chromophore, a carboxy and an amino substituent are located allowing for oligomerization via peptide coupling. The proof of constitution and the conformational preferences about the biaryl-like axis were established by means of X-ray analyses of the corresponding nitro derivatives 10 and 11. Thus, the uracil bases are propeller-twisted relative to the thiophene core, and bidentate H-bonds occur between two uracil bases in the crystals. The two amino-acid building blocks 12 and 13 were coupled to give the dimers 15 and 16 using dicyclohexylcarbodiimide (DCC) in THF/LiCl and DMF, respectively. While the dimer 15 showed no atropisomerism on the NMR time scale at room temperature, its isomer 16 occurred as distinct diastereoisomers due to the hindered rotation around its biaryl-like axis. Variable-temperature 1H-NMR experiments allowed to determine a rotational barrier of 19 ± 1 kcal/mol in 16. The experimental data were complemented by AM1 calculations.

Estimation of the postmortem interval by means of ¹H MRS of decomposing brain tissue: influence of ambient temperature

Standard methods for the estimation of the postmortem interval (PMI, time since death), based on the cooling of the corpse, are limited to about 48 h after death. As an alternative, noninvasive postmortem observation of alterations of brain metabolites by means of (1)H MRS has been suggested for an estimation of the PMI at room temperature, so far without including the effect of other ambient temperatures. In order to study the temperature effect, localized (1)H MRS was used to follow brain decomposition in a sheep brain model at four different temperatures between 4 and 26°C with repeated measurements up to 2100 h postmortem. The simultaneous determination of 25 different biochemical compounds at each measurement allowed the time courses of concentration changes to be followed. A sudden and almost simultaneous change of the concentrations of seven compounds was observed after a time span that decreased exponentially from 700 h at 4°C to 30 h at 26°C ambient temperature. As this represents, most probably, the onset of highly variable bacterial decomposition, and thus defines the upper limit for a reliable PMI estimation, data were analyzed only up to this start of bacterial decomposition. As 13 compounds showed unequivocal, reproducible concentration changes during this period while eight showed a linear increase with a slope that was unambiguously related to ambient temperature. Therefore, a single analytical function with PMI and temperature as variables can describe the time courses of metabolite concentrations. Using the inverse of this function, metabolite concentrations determined from a single MR spectrum can be used, together with known ambient temperatures, to calculate the PMI of a corpse. It is concluded that the effect of ambient temperature can be reliably included in the PMI determination by (1)H MRS.

Simulating the temperature and precipitation signal in an Alpine ice core

Accumulation and delta O-18 data from Alpine ice cores provide information on past temperature and precipitation. However, their correlation with seasonal or annual mean temperature and precipitation at nearby sites is often low. This is partly due to the irregular sampling of the atmosphere by the ice core (i.e. ice cores almost only record precipitation events and not dry periods) and the possible incongruity between annual layers and calendar years. Using daily meteorological data from a nearby station and reanalyses, we replicate the ice core from the Grenzgletscher (Switzerland, 4200m a.s.l.) on a sample-by-sample basis by calculating precipitation-weighted temperature (PWT) over short intervals. Over the last 15 yr of the ice core record, accumulation and delta O-18 variations can be well reproduced on a sub-seasonal scale. This allows a wiggle-matching approach for defining quasi-annual layers, resulting in high correlations between measured quasi-annual delta O-18 and PWT. Further back in time, the agreement deteriorates. Nevertheless, we find significant correlations over the entire length of the record (1938-1993) of ice core delta O-18 with PWT, but not with annual mean temperature. This is due to the low correlations between PWT and annual mean temperature, a characteristic which in ERA-Interim reanalysis is also found for many other continental mid-to-high-latitude regions. The fact that meteorologically very different years can lead to similar combinations of PWT and accumulation poses limitations to the use of delta O-18 from Alpine ice cores for temperature reconstructions. Rather than for reconstructing annual mean temperature, delta O-18 from Alpine ice cores should be used to reconstruct PWT over quasi-annual periods. This variable is reproducible in reanalysis or climate model data and could thus be assimilated into conventional climate models.

A chrysophyte stomatocyst-based reconstruction of cold-season air temperature from Alpine Lake Silvaplana (AD 1500–2003); methods and concepts for quantitative inferences

Relatively little is known about past cold-season temperature variability in high-Alpine regions because of a lack of natural cold-season temperature proxies as well as under-representation of high-altitude sites in meteorological, early-instrumental and documentary data sources. Recent studies have shown that chrysophyte stomatocysts, or simply cysts (sub-fossil algal remains of Chrysophyceae and Synurophyceae), are among the very few natural proxies that can be used to reconstruct cold-season temperatures. This study presents a quantitative, high-resolution (5-year), cold-season (Oct–May) temperature reconstruction based on sub-fossil chrysophyte stomatocysts in the annually laminated (varved) sediments of high-Alpine Lake Silvaplana, SE Switzerland (1,789 m a.s.l.), since AD 1500. We first explore the method used to translate an ecologically meaningful variable based on a biological proxy into a simple climate variable. A transfer function was applied to reconstruct the ‘date of spring mixing’ from cyst assemblages. Next, statistical regression models were tested to convert the reconstructed ‘dates of spring mixing’ into cold-season surface air temperatures with associated errors. The strengths and weaknesses of this approach are thoroughly tested. One much-debated, basic assumption for reconstructions (‘stationarity’), which states that only the environmental variable of interest has influenced cyst assemblages and the influence of confounding variables is negligible over time, is addressed in detail. Our inferences show that past cold-season air-temperature fluctuations were substantial and larger than those of other temperature reconstructions for Europe and the Alpine region. Interestingly, in this study, recent cold-season temperatures only just exceed those of previous, multi-decadal warm phases since AD 1500. These findings highlight the importance of local studies to assess natural climate variability at high altitudes.

Dependence of Eemian Greenland temperature reconstructions on the ice sheet topography

The influence of a reduced Greenland Ice Sheet (GrIS) on Greenland's surface climate during the Eemian interglacial is studied using a set of simulations with different GrIS realizations performed with a comprehensive climate model. We find a distinct impact of changes in the GrIS topography on Greenland's surface air temperatures (SAT) even when correcting for changes in surface elevation, which influences SAT through the lapse rate effect. The resulting lapse-rate-corrected SAT anomalies are thermodynamically driven by changes in the local surface energy balance rather than dynamically caused through anomalous advection of warm/cold air masses. The large-scale circulation is indeed very stable among all sensitivity experiments and the Northern Hemisphere (NH) flow pattern does not depend on Greenland's topography in the Eemian. In contrast, Greenland's surface energy balance is clearly influenced by changes in the GrIS topography and this impact is seasonally diverse. In winter, the variable reacting strongest to changes in the topography is the sensible heat flux (SHF). The reason is its dependence on surface winds, which themselves are controlled to a large extent by the shape of the GrIS. Hence, regions where a receding GrIS causes higher surface wind velocities also experience anomalous warming through SHF. Vice-versa, regions that become flat and ice-free are characterized by low wind speeds, low SHF, and anomalous low winter temperatures. In summer, we find surface warming induced by a decrease in surface albedo in deglaciated areas and regions which experience surface melting. The Eemian temperature records derived from Greenland proxies, thus, likely include a temperature signal arising from changes in the GrIS topography. For the Eemian ice found in the NEEM core, our model suggests that up to 3.1 °C of the annual mean Eemian warming can be attributed to these topography-related processes and hence is not necessarily linked to large-scale climate variations.

Revisiting the ISN Flow Parameters, using a variable IBEX pointing strategy

The Interstellar Boundary Explorer (IBEX) has observed the interstellar neutral (ISN) gas flow over the past 6 yr during winter/spring when the Earth's motion opposes the ISN flow. Since IBEX observes the interstellar atom trajectories near their perihelion, we can use an analytical model based upon orbital mechanics to determine the interstellar parameters. Interstellar flow latitude, velocity, and temperature are coupled to the flow longitude and are restricted by the IBEX observations to a narrow tube in this parameter space. In our original analysis we found that pointing the spacecraft spin axis slightly out of the ecliptic plane significantly influences the ISN flow vector determination. Introducing the spacecraft spin axis tilt into the analytical model has shown that IBEX observations with various spin axis tilt orientations can substantially reduce the range of acceptable solutions to the ISN flow parameters as a function of flow longitude. The IBEX operations team pointed the IBEX spin axis almost exactly within the ecliptic plane during the 2012-2014 seasons, and about 5° below the ecliptic for half of the 2014 season. In its current implementation the analytical model describes the ISN flow most precisely for the spin axis orientation exactly in the ecliptic. This analysis refines the derived ISN flow parameters with a possible reconciliation between velocity vectors found with IBEX and Ulysses, resulting in a flow longitude lambda∞ = 74.°5 ± 1.°7 and latitude beta∞ = -5.°2 ± 0.°3, but at a substantially higher ISN temperature than previously reported.