The Scope of Appellate Review in Criminal Cases: Who Has the Final Word?

The Scope of Appellate Review in Criminal Cases: Who has the final word

Chemical Adsorption of HF, HCl, and H2O onto YF3 and Isostructural HoF3 Surfaces by First Principles

The two elements, yttrium and holmium, form a geochemical twin pair as their cations possess equivalent ratios of charge to radius. However, despite their equal electrostatics, a subtle difference in their fluoride or chloride affinity is known within solutions. In this work, we investigated whether this affinity gap is also present within the solid phase and how it depends on the surface configuration. We modeled adsorptions onto β-YF3 (waimirite) and isostructural β-HoF3 by periodic density functional theory. To draw conclusions on the affinity toward fluoride and chloride vs. water, adsorbates of HF, HCl, or H2O onto any of the four highly abundant surfaces of (010), (100), (011), and (101) were studied. Among others, the conformational landscape was explored by 200 ps of ab initio molecular dynamics. For stoichiometric surfaces of both MF3, we indeed found stronger adsorptions for HF than HCl. All (hkl)⋅H2O showed slightly stronger adsorption energies for HoF3, while for HF and HCl, the metal preferences varied by the surface. While (100) showed the strongest preference for HoF3, (101) preferred YF3 by the same magnitude

Correction: Anders et al. First Principle Surface Analysis of YF3 and Isostructural HoF3. Materials 2022, 15, 6048

In the original publication [1], there was a mistake in Table 2 and Figure 2 as published. Within Table 2, the coordination numbers of the two stoichiometric terminations of surface (011) have been flipped [showing (011)-1 and (011)-2 with 6,6,8,8 and 7,7,9,9, respectively]. Figure 2 showed the surface of (011)-2 in the first row, third image with the same incorrect coordination numbers of 7,7,9,9 instead of 6,6,8,8. The authors state that the scientific conclusions are unaffected. This correction was approved by the Academic Editor. The original publication has also been updated

First Principle Surface Analysis of YF3 and Isostructural HoF3

The trifluorides of the two high field strength elements yttrium and holmium are studied by periodic density functional theory. As a lanthanide, holmium also belongs to the group of rare earth elements (REE). Due to their equivalent geochemical behavior, both elements form a geochemical twin pair and consequently, yttrium is generally associated with the REE as REE+Y. Interestingly, it has been found that DFT/DFT+U describe bulk HoF3 best, when the 4f-electrons are excluded from the valence region. An extensive surface stability analysis of YF3 (PBE) and HoF3 (PBE+Ud/3 eV/4f-in-core) using two-dimensional surface models (slabs) is performed. All seven low-lying Miller indices surfaces are considered with all possible stoichiometric or substoichiometric terminations with a maximal fluorine-deficit of two. This leads to a scope of 24 terminations per compound. The resulting Wulff plots consists of seven surfaces with 5–26% abundance for YF3 and six surfaces with 6–34% for HoF3. The stoichiometric (010) surface is dominating in both compounds. However, subtle differences have been found between these two geochemical twins

Direct angiotensin AT2 receptor stimulation using a novel AT2 receptor agonist, compound 21, evokes neuroprotection in conscious hypertensive rats

Background: In this study, the neuroprotective effect of a novel nonpeptide AT2R agonist, C21, was examined in a conscious model of stroke to verify a class effect of AT2R agonists as neuroprotective agents. Methods and Results: Spontaneously hypertensive rats (SHR) were pre-treated for 5 days prior to stroke with C21 alone or in combination with the AT2R antagonist PD123319. In a separate series of experiments C21 was administered in a series of 4 doses commencing 6 hours after stroke. A focal reperfusion model of ischemia was induced in conscious SHR by administering endothelin-1 to the middle cerebral artery (MCA). Motor coordination was assessed at 1 and 3 days after stroke and post mortem analyses of infarct volumes, microglia activation and neuronal survival were performed at 72 hours post MCA occlusion. When given prior to stroke, C21 dose dependently decreased infarct volume, which is consistent with the behavioural findings illustrating an improvement in motor deficit. During the pre-treatment protocol C21 was shown to enhance microglia activation, which are likely to be evoking protection by releasing brain derived neurotrophic factor. When drug administration was delayed until 6 hours after stroke, C21 still reduced brain injury. Conclusion: These results indicate that centrally administered C21 confers neuroprotection against stroke damage. This benefit is likely to involve various mechanisms, including microglial activation of endogenous repair and enhanced cerebroperfusion. Thus, we have confirmed the neuroprotective effect of AT2R stimulation using a nonpeptide compound which highlights the clinical potential of the AT2R agonists for future development

Results for the 2017 VIMS Industry Cooperative Surveys of the Mid-Atlantic, Nantucket Lightship Closed Area, and Closed Area II Resource Areas

The Virginia Institute of Marine Science (VIMS) conducted high resolution sea scallop dredge surveys of the entire Mid-Atlantic (MAB) sea scallop resource area, the Nantucket Lightship (NLCA) access area and surrounds, and the CA II access area and Extension Closure during May-July of 2017 (Figure 1). These surveys were funded by the Sea Scallop Research Set-Aside Program (RSA). Exploitable biomass for each survey is shown in Table 1 for each spatially explicit SAMS (Scallop Area Management Simulator) model area (Figure 2-4). SAMS areas account for differences in recruitment, vital rates, and fishing effort. At the time of the surveys, exploitable biomass estimated from the commercial dredge was 13,711 mt or 30.2 million pounds for the Open Elephant Truck (ET-Open) SAMS area and 8,907 mt or 19.6 million pounds in Elephant Trunk Flex (ET-Flex) SAMS area. For open access area in the Long Island (LI) SAMS area, exploitable biomass was estimated at 10,711 mt or 23.6 million pounds. In the NLCA, the exploitable biomass in the northern region (NLS_AC_N area in Table 1) was 5,600 mt or 12.3 million pounds. Exploitable biomass in the CAII survey traditional access area (CAII_S_AC in Table 1) was 6,296 mt or 13.9 million pounds

Stability of Hydroxo/Oxo/Fluoro Zirconates vs. Hafniates - A DFT Study

We performed density functional theory (DFT) calculations on binary and ternary oxo/fluoro crystals of the geochemical twin pair zirconium and hafnium to evaluate and compare their stabilities. This is the first DFT study on bulk ZrF4 or HfF4, as well as on a hypothetical ZrOF2 or HfOF2 bulk crystal. For α-MO2, β-MF4 and MOF2, we have found significantly higher cohesive energies for the respective hafnium species. This suggests a considerable gap in affinity toward fluorine and oxygen between the twin pair in the solid state. In agreement with experimental findings, this gap is slightly more pronounced for fluorine. This study is also the first to evaluate the theoretical, endothermic mono-hydroxylation of the respective fluorides or oxyfluorides to model the difference in affinity toward fluoride versus hydroxide. For these, we could also find a slight energetic preference for the hafnium compound

Low concentrations of perfluoroalkyl acids (PFAAs) in municipal drinking water associated with serum PFAA concentrations in Swedish adolescents

While highly contaminated drinking water (DW) is a major source of exposure to perfluoroalkyl acids (PFAAs), the contribution of low-level contaminated DW (i.e. < 10 ng/L of individual PFAAs) to PFAA body burdens has rarely been studied. To address this knowledge gap, we evaluated the association between concentrations of perflurooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexane sulfonic acid (PFHxS) and perfluorooctane sulfonic acid (PFOS), and their sum (& sum;(4)PFAAs) in DW and serum in Swedish adolescents using weighted least squares regression. We paired serum PFAA concentrations in adolescents (age 10-21 years, n = 790) from the dietary survey Riksmaten Adolescents 2016-17 (RMA) with mean PFAA concentrations in water samples collected in 2018 from waterworks (n = 45) supplying DW to the participant residential and school addresses. The median concentrations of individual PFAAs in DW were < 1 ng/L. Median concentrations of PFNA and PFHxS in serum were < 1 ng/g, while those of PFOA and PFOS were 1-2 ng/g. Significant positive associations between PFAA concentrations in DW and serum were found for all four PFAAs and & sum;(4)PFAAs, with estimated serum/DW concentration ratios ranging from 210 (PFOA) to 670 (PFHxS), taking exposure from sources other than DW (background) into consideration. The mean concentrations of PFHxS and & sum;(4)PFAA in DW that would likely cause substantially elevated serum concentrations above background variation were estimated to 0.9 ng/L and 2.4 ng/L, respectively. The European Food Safety Authority has determined a health concern concentration of 6.9 ng & sum;(4)PFAAs/mL serum. This level was to a large degree exceeded by RMA participants with DW & sum;(4)PFAA concentrations above the maximum limits implemented in Denmark (2 ng & sum;(4)PFAAs/L) and Sweden (4 ng & sum;(4)PFAAs/L) than by RMA participants with DW concentrations below the maximum limits. In conclusion, PFAA exposure from low-level contaminated DW must be considered in risk assessment for adolescents

Chemical bonding of HF, HCl, and H2O onto YF3 surfaces: quantification by first principles

The surfaces of waimirite β-YF3 have been studied for their fluorine and chlorine versus water affinity. Bonding patterns of HF, HCl, and H2O chemically adsorbed onto surfaces of (010), (100), (011), and (101) have been quantified by density functional theory applying energy decomposition analysis. We found that the adsorption of H2O is dominated by about 65% of electrostatics, which causes a low surface sensitivity and weak interactions. On the contrary, the adsorptions of HF and HCl are driven by strong hydrogen bonds resulting in a highly surface-dependent ratio of 30–60% electrostatic versus orbital contribution. Among the stoichiometric surfaces, the shortest and strongest hydrogen bonds and consequently most covalent bonding patterns are found within YF3 HCl. However, when including the preparation energy, each surface favors the adsorption of HF over HCl, which reproduces the higher affinity of yttrium towards fluoride over chloride, previously known for solutions, also for the solid state