Theoretical study on the protonation of AZA-aromatics

The protonation of azanaphthalenes and azabenzenes has been studied theoretically using CNDO/2 wavefunctions and perturbation theory in order to examine the correlation between pKa values and quantum-mechanical quantities

Diazanaphthalenes: A 13C NMR investigation on the site of protonation and pKa values

The pH dependence of the 13C chemical shifts (δ) of the diazanaphthalenes has been recorded. From this dependence the pKa values have been determined using the Henderson-Hasselbach equation. The change in 13C chemical shifts under the influence of nitrogen protonation (Δδ) has been predicted using the Δδ values of quinoline and isoquinoline. The correlation between observed and expected Δδ values of the symmetric diazanaphthalenes is very good. Assuming these changes in chemical shifts to be of general validity, the site of protonation in the asymmetric diazanaphthalenes has been determined by comparison of the expected Δδ values for α- and ß-nitrogen protonation with the observed ones. The site of protonation for 1,6- and 1,7-naphthyridine is the ß-nitrogen atom, whereas for cinnoline both monoprotonated species are present in a significant amount

Cretaceous slab break-off in the Pyrenees: Iberian plate kinematics in paleomagnetic and mantle reference frames

AbstractThe Pyrenees at the Iberia–Europe collision zone contain sediments showing Albian–Cenomanian high-temperature metamorphism, and coeval alkaline magmatic rocks. Stemming from different views on Jurassic–Cretaceous Iberian microplate kinematics, two schools of thought exist on the trigger of this thermal pulse: one invoking hyperextension of the Iberian and Eurasian margins, the other suggesting slab break-off. Competing scenarios for Mesozoic Iberian motion compatible with Pyrenean geology, comprise (1) transtensional eastward motion of Iberia versus Eurasia, or (2) strike-slip motion followed by orthogonal extension, both favoring hyperextension-related heating, and (3) scissor-style opening of the Bay of Biscay coupled with subduction in the Pyrenean realm, favoring the slab break-off hypothesis. We test these kinematic scenarios for Iberia against a newly compiled paleomagnetic dataset and conclude that the scissor-type scenario is the only one consistent with a well-defined ~35° counterclockwise rotation of Iberia during the Early Aptian. We proceed to show that when taking absolute plate motions into account, Aptian oceanic subduction in the Pyrenees followed by Late Aptian–Early Albian slab break-off should leave a slab remnant in the present-day mid-mantle below NW Africa. Mantle tomography shows the Reggane anomaly that matches the predicted position and dimension of such a slab remnant between 1900 and 1500km depth below southern Algeria. Mantle tomography is therefore consistent with the scissor-type opening of the Bay of Biscay coupled with subduction in the Pyrenean realm. Slab break-off may thus explain high-temperature metamorphism and alkaline magmatism during the Albian–Cenomanian in the Pyrenees, whereas hyperextension that exhumed Pyrenean mantle bodies occurred much earlier, in the Jurassic

Sedimentary geology of the Middle Carboniferous of the Donbas region (Dniepr-Donets basin, Ukraine)

Peer reviewedPublisher PD

Subduction and Slab Detachment Under Moving Trenches During Ongoing India-Asia Convergence

The dynamics of slab detachment and associated geological fingerprints have been inferred from various numerical and analog models. These invariably use a setup with slab-pull-driven convergence in which a slab detaches below a mantle-stationary trench after the arrest of plate convergence due to arrival of continental lithosphere. In contrast, geological reconstructions show that post-detachment plate convergence is common and that trenches and sutures are rarely mantle-stationary during detachment. Here, we identify the more realistic kinematic context of slab detachment using the example of the India-Asia convergent system. We first show that only the India and Himalayas slabs (from India's northern margin) and the Carlsberg slab (from the western margin) unequivocally detached from Indian lithosphere. Several other slabs below the Indian Ocean do not require a Neotethyan origin and may be of Mesotethys and Paleotethys origin. Additionally, the still-connected slabs are being dragged together with the Indian plate forward (Hindu Kush) or sideways (Burma, Chaman) through the mantle. We show that Indian slab detachment occurred at moving trenches during ongoing plate convergence, providing more realistic geodynamic conditions for use in future numerical and analog experiments. We identify that the actively detaching Hindu Kush slab is a type-example of this setting, whilst a 25–13 Ma phase of shallow detachment of the Himalayas slab, here reconstructed from plate kinematics and tomography, agrees well with independent, published geological estimates from the Himalayas orogen of slab detachment. The Sulaiman Ranges of Pakistan may hold the geological signatures of detachment of the laterally dragged Carlsberg slab

Long-term Phanerozoic global mean sea level: Insights from strontium isotope variations and estimates of continental glaciation

Global mean sea level is a key component within the fields of climate and oceanographic modelling in the Anthropocene. Hence, an improved understanding of eustatic sea level in deep time aids in our understanding of Earth's paleoclimate and may help predict future climatological and sea level changes. However, long-term eustatic sea level reconstructions are hampered because of ambiguity in stratigraphic interpretations of the rock record and limitations in plate tectonic modelling. Hence the amplitude and timescales of Phanerozoic eustasy remains poorly constrained. A novel, independent method from stratigraphic or plate modelling methods, based on estimating the effect of plate tectonics (i.e., mid-ocean ridge spreading) from the 87Sr/86Sr record led to a long-term eustatic sea level curve, but did not include glacio-eustatic drivers. Here, we incorporate changes in sea level resulting from variations in seawater volume from continental glaciations at time steps of 1 Myr. Based on a recent compilation of global average paleotemperature derived from δ18O data, paleo-Köppen zones and paleogeographic reconstructions, we estimate ice distribution on land and continental shelf margins. Ice thickness is calibrated with a recent paleoclimate model for the late Cenozoic icehouse, yielding an average ∼1.4 km thickness for land ice, ultimately providing global ice volume estimates. Eustatic sea level variations associated with long-term glaciations (>1 Myr) reach up to ∼90 m, similar to, and is at times dominant in amplitude over plate tectonic-derived eustasy. We superimpose the long-term sea level effects of land ice on the plate tectonically driven sea level record. This results in a Tectono-Glacio-Eustatic (TGE) curvefor which we describe the main long-term (>50 Myr) and residual trends in detail

The soluble receptor for advanced glycation end products is potentially predictive of pulmonary arterial hypertension in systemic sclerosis

IntroductionPulmonary arterial hypertension (PAH) and interstitial lung disease (ILD) are the leading causes of death in systemic sclerosis (SSc). Until now, no prospective biomarker to predict new onset of SSc-ILD or SSc-PAH in patients with SSc has reached clinical application. In homeostasis, the receptor for advanced glycation end products (RAGE) is expressed in lung tissue and involved in cell-matrix adhesion, proliferation and migration of alveolar epithelial cells, and remodeling of the pulmonary vasculature. Several studies have shown that sRAGE levels in serum and pulmonary tissue vary according to the type of lung-related complication. Therefore, we investigated levels of soluble RAGE (sRAGE) and its ligand high mobility group box 1 (HMGB1) in SSc and their abilities to predict SSc-related pulmonary complications.MethodsOne hundred eighty-eight SSc patients were followed retrospectively for the development of ILD, PAH, and mortality for 8 years. Levels of sRAGE and HMGB1 were measured in serum by ELISA. Kaplan-Meier survival curves were performed to predict lung events and mortality and event rates were compared with a log-rank test. Multiple linear regression analysis was performed to examine the association between sRAGE and important clinical determinants.ResultsAt baseline, levels of sRAGE were significantly higher in SSc-PAH-patients (median 4099.0 pg/ml [936.3-6365.3], p = 0.011) and lower in SSc-ILD-patients (735.0 pg/ml [IQR 525.5-1988.5], p = 0.001) compared to SSc patients without pulmonary involvement (1444.5 pg/ml [966.8-2276.0]). Levels of HMGB1 were not different between groups. After adjusting for age, gender, ILD, chronic obstructive pulmonary disease, anti-centromere antibodies, the presence of puffy fingers or sclerodactyly, use of immunosuppression, antifibrotic therapy, or glucocorticoids, and use of vasodilators, higher sRAGE levels remained independently associated with PAH. After a median follow-up of 50 months (25-81) of patients without pulmonary involvement, baseline sRAGE levels in the highest quartile were predictive of development of PAH (log-rank p = 0.01) and of PAH-related mortality (p = 0.001).ConclusionsHigh systemic sRAGE at baseline might be used as a prospective biomarker for patients with SSc at high risk to develop new onset of PAH. Moreover, high sRAGE levels could predict lower survival rates due to PAH in patients with SSc

From Passive to Active:Unpacking the EU’s New Role in Promoting Peace between Azerbaijan and Armenia

This article analyses the European Union’s (EU) increased involvement in promoting peace between Armenia and Azerbaijan following the Second Karabakh War in 2020. While the EU’s previous (indirect) engagement was shadowed by its member state France’s cochairing role within the Minsk Group, its recent diplomatic efforts and visibility signify a shift towards more active involvement in the South Caucasus region. This article explores the motivations behind the EU’s engagement, including its political and economic interests in the region. Additionally, the article highlights the challenges that the EU faces in promoting lasting peace in this region. Furthermore, this article provides policyrecommendations for the EU to promote peace and stability in the region. These include maintaining a consistent stance against separatism, drawing on its own experience with resolving conflicts within the Union, and increasing its financial investments in trade, infrastructure, and renewable energy production. By following these recommendations, the EU can strengthen its influence in the South Caucasus and promote lasting peace in the region