Thermodynamic parameters including acid dissociation constants for bromochlorophenols (BCPs)

This contribution reports standard gas-phase enthalpies of formation (ΔfH°298), entropies (S°298), and heat capacities (Cp°(T)) for all plausible 64 bromochlorophenols (BCPs) at the M062X meta hybrid level using a polarized basis set of 6-311+G(d,p). Isodesmic work reactions served to calculate the standard enthalpies of formation for all bromochlorophenol molecules and several bromochlorophenoxy radicals. Standard entropies and heat capacities comprise correction terms due to the treatment of O-H bonds as hindered rotors. Values of the bond dissociation enthalpies (BDHs) of O-H bonds, calculated for a selected series of bromochlorophenols, vary slightly with the change in the pattern and degree of halogenation of the phenyl ring. A thermodynamic cycle facilitated the estimation of pKa values, based on the calculated solvation and gas-phase deprotonation energies. We estimated the solvation energies of 19 out of 64 BCPs and their respective anions based on the integral equation formalism polarizable continuum model using optimized structures in the aqueous phase. Values of pKa decrease significantly from around 9 for monohalogenated to around 3 for pentahalogenated phenols

IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater - Revised and updated. Part 8. C9 hydrocarbons with water

The mutual solubility and related liquid-liquid equilibria of C9 hydrocarbons with water are exhaustively and critically reviewed. Reports of the experimental determination of solubility in 18 chemically distinct binary systems that appeared in the primary literature prior to the end of 2002 are compiled. For 8 systems, sufficient data are available to allow critical evaluation. All data are expressed as mass percent and mole fraction, as well as the originally reported units. In addition to the standard evaluation criteria used throughout the Solubility Date Series, a new method based on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons was used

IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater-revised and updated. Part 5. C7 hydrocarbons with water and heavy water

The mutual solubility and related liquid-liquid equilibria of C7 hydrocarbons with water and heavy water are exhaustively and critically reviewed. Reports of experimental determination of solubility in 23 chemically distinct binary systems that appeared in the primary literature prior to end of 2002 are compiled. For 9 systems sufficient data are available to allow critical evaluation. All data are expressed as mass percent and mole fraction as well as the originally reported units. In addition to the standard evaluation criteria used throughout the Solubility Data Series, a new method based on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons was used

4-Bromo-N-phenyl­aniline

In the title compound, C12H10BrN, the dihedral angle between the benzene rings is 52.5 (1)°, whereas the pitch angles, or the angles between the mean plane of each aryl group ‘propeller blade’ and the plane defined by the aryl bridging C—N—C angle, are 19.6 (2) and 36.2 (3)°. While the N—H group is not involved in hydrogen-bonding inter­actions, the structure exhibits a network of inter­molecular C—H⋯π and N—H⋯π inter­actions

Bathypelagic particle flux signatures from a suboxic eddy in the oligotrophic tropical North Atlantic: production, sedimentation and preservation

Particle fluxes at the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic for the period December 2009 until May 2011 are discussed based on bathypelagic sediment trap time-series data collected at 1290 and 3439 m water depth. The typically oligotrophic particle flux pattern with weak seasonality is modified by the appearance of a highly productive and low oxygen (minimum concentration below 2 µmol kg−1 at 40 m depth) anticyclonic modewater eddy (ACME) in winter 2010. The eddy passage was accompanied by unusually high mass fluxes of up to 151 mg m−2 d−1, lasting from December 2009 to May 2010. Distinct biogenic silica (BSi) and organic carbon flux peaks of ∼ 15 and 13.3 mg m−2 d−1, respectively, were observed in February–March 2010 when the eddy approached the CVOO. The flux of the lithogenic component, mostly mineral dust, was well correlated with that of organic carbon, in particular in the deep trap samples, suggesting a tight coupling. The lithogenic ballasting obviously resulted in high particle settling rates and, thus, a fast transfer of epi-/meso-pelagic signatures to the bathypelagic traps. We suspect that the two- to three-fold increase in particle fluxes with depth as well as the tight coupling of mineral dust and organic carbon in the deep trap samples might be explained by particle focusing processes within the deeper part of the eddy. Molar C : N ratios of organic matter during the ACME passage were around 18 and 25 for the upper and lower trap samples, respectively. This suggests that some productivity under nutrient (nitrate) limitation occurred in the euphotic zone of the eddy in the beginning of 2010 or that a local nitrogen recycling took place. The δ15N record showed a decrease from 5.21 to 3.11 ‰ from January to March 2010, while the organic carbon and nitrogen fluxes increased. The causes of enhanced sedimentation from the eddy in February/March 2010 remain elusive, but nutrient depletion and/or an increased availability of dust as a ballast mineral for organic-rich aggregates might have contributed. Rapid remineralisation of sinking organic-rich particles could have contributed to oxygen depletion at shallow depth. Although the eddy formed in the West African coastal area in summer 2009, no indications of coastal flux signatures (e.g. from diatoms) were found in the sediment trap samples, confirming the assumption that the suboxia developed within the eddy en route. However, we could not detect biomarkers indicative of the presence of anammox (anaerobic ammonia oxidation) bacteria or green sulfur bacteria thriving in photic zone suboxia/hypoxia, i.e. ladderane fatty acids and isorenieratene derivatives, respectively. This could indicate that suboxic conditions in the eddy had recently developed and/or the respective bacterial stocks had not yet reached detection thresholds. Another explanation is that the fast-sinking organic-rich particles produced in the surface layer did not interact with bacteria from the suboxic zone below. Carbonate fluxes dropped from ∼ 52 to 21.4 mg m−2 d−1 from January to February 2010, respectively, mainly due to reduced contribution of shallow-dwelling planktonic foraminifera and pteropods. The deep-dwelling foraminifera Globorotalia menardii, however, showed a major flux peak in February 2010, most probably due to the suboxia/hypoxia. The low oxygen conditions forced at least some zooplankton to reduce diel vertical migration. Reduced “flux feeding” by zooplankton in the epipelagic could have contributed to the enhanced fluxes of organic materials to the bathypelagic traps during the eddy passage. Further studies are required on eddy-induced particle production and preservation processes and particle focusin

Characterization of particulate organic matter in the Lena River delta and adjacent nearshore zone, NE Siberia – Part 2: Lignin-derived phenol compositions

The Lena River in central Siberia is one of the major pathways translocating terrestrial organic matter (OM) from its vast catchment area to the coastal zone of the Laptev Sea and the Arctic Ocean. The permafrost soils of its far south-stretching catchment, which store huge amounts of OM, will most likely respond differently to climate warming and remobilize previously frozen OM with distinct properties specific for the source vegetation and soil. To characterize the material discharged by the Lena River, we analyzed the lignin phenol composition in total suspended matter (TSM) from surface water collected in spring and summer, surface sediments from Buor Khaya Bay along with soils from the Lena Delta’s first (Holocene) and third terraces (Pleistocene ice complex), and plant samples. Our results show that lignin-derived cinnamyl : vanillyl (C / V) and syringyl : vanillyl (S / V) ratios are > 0.14 and 0.25, respectively, in TSM and surface sediments, whereas in delta soils they are > 0.16 and > 0.51, respectively. These lignin compositions are consistent with significant inputs of organic matter from non-woody angiosperm sources mixed with organic matter derived from woody gymnosperm sources. We applied a simple linear mixing model based on the C / V and S / V ratios, and the results indicate the organic matter in delta TSM samples and Buor Khaya Bay surface sediments contain comparable contributions from gymnosperm material, which is primarily derived from the taiga forests south of the delta, and angiosperm material typical for tundra vegetation. Considering the small catchment area covered by tundra (~12 %), the input is substantial and tundra-derived OM input is likely to increase in a warming Arctic. The similar and high acid to aldehyde ratios of vanillyl and syringyl (Ad / Al[subscript V, S]) in Lena Delta summer TSM (> 0.7 and > 0.5, respectively) and Buor Khaya Bay surface sediments (> 1.0 and > 0.9, respectively) suggest that the OM is highly degraded and Lena River summer TSM could be a possible source of the surface sediments. The Ad / Al[subscript V, S] ratios of the first and third delta terraces were generally lower (mean ratios > 0.4 and > 0.4, respectively) than summer TSM and surface sediments. This implies that TSM contains additional contributions from a more degraded OM source (southern catchment and/or finer more degraded particle size). Alternatively, OM degradation on land after permafrost thawing and subaqueously during transport and sedimentation could be considerable. Despite the high natural heterogeneity of OM stored in delta soils and exported by the Lena River, the catchment-characteristic vegetation is reflected by the lignin biomarker composition. Climate-warming-related changes in the Lena River catchment may be detectable in changing lignin biomarker composition and diagenetic alteration

Exploring face perception in disorders of development: evidence from Williams syndrome and autism

Individuals with Williams syndrome (WS) and autism are characterized by different social phenotypes but have been said to show similar atypicalities of face-processing style. Although the structural encoding of faces may be similarly atypical in these two developmental disorders, there are clear differences in overall face skills. The inclusion of both populations in the same study can address how the profile of face skills varies across disorders. The current paper explored the processing of identity, eye-gaze, lip-reading, and expressions of emotion using the same participants across face domains. The tasks had previously been used to make claims of a modular structure to face perception in typical development. Participants with WS (N=15) and autism (N=20) could be dissociated from each other, and from individuals with general developmental delay, in the domains of eye-gaze and expression processing. Individuals with WS were stronger at these skills than individuals with autism. Even if the structural encoding of faces appears similarly atypical in these groups, the overall profile of face skills, as well as the underlying architecture of face perception, varies greatly. The research provides insights into typical and atypical models of face perception in WS and autism

Expedition 306 summary

The overall aim of the North Atlantic paleoceanography study of Integrated Ocean Drilling Program Expedition 306 is to place late Neogene–Quaternary climate proxies in the North Atlantic into a chronology based on a combination of geomagnetic paleointensity, stable isotope, and detrital layer stratigraphies, and in so doing generate integrated North Atlantic millennial-scale stratigraphies for the last few million years. To reach this aim, complete sedimentary sections were drilled by multiple advanced piston coring directly south of the central Atlantic “ice-rafted debris belt” and on the southern Gardar Drift. In addition to the North Atlantic paleoceanography study, a borehole observatory was successfully installed in a new ~180 m deep hole close to Ocean Drilling Program Site 642, consisting of a circulation obviation retrofit kit to seal the borehole from the overlying ocean, a thermistor string, and a data logger to document and monitor bottom water temperature variations through time

Pseudocholinesterase as a biomarker for untreated Wilson's disease

The aim of this study was to demonstrate that pseudocholinesterase (CHE) serum level is a useful diagnostic biomarker for untreated Wilson's disease (WD). Between 2013 and 2019, about 75 patients were referred to the outpatient department of the University of Düsseldorf with suspected Wilson's disease. In 31 patients with suspected Wilson's disease (WD-SUS-group), WD was excluded by means of investigations other than analysis of blood and urine. A total of 27 parameters of blood and urine in these 31 patients were compared to those of 20 de novo patients with manifest WD (WD-DEF-group), which parameter showed the highest significance level of difference between the WD-DEF-group and the WD-SUS-group. Thereafter, receiver operating characteristics (ROC-curves) were analyzed to evaluate which parameter showed the largest area under the curve (AUC) to detect WD. Finally, a logistic regression analysis was performed to analyze which combination of parameters allowed the best classification of the 51 patients either into the WD-DEF-group or into the WD-SUS-group. CHE showed the highest significance level for a difference between the WD-DEF- and WD-SUS-group, had the highest AUC, and, in combination with ceruloplasmin, allowed 100% correct classification. Without CHE, no other combination of parameters reached this level of correct classification. After the initiation of treatment, which regularly results in an improvement in CHE, the high diagnostic accuracy of this biomarker was lost. Cholinesterase turns out to be an excellent biomarker for differentiation between untreated de novo patients with manifest WD and heterozygotic gene carriers