Core Formation Research Articles

SAXS, DLS, and MD studies of the Rg/Rh ratio for swollen and collapsed dendrimers.

The radius of gyration, Rg, and the hydrodynamic radius, Rh, are the main experimental parameters that characterize the size of linear and branched macromolecules. In the case of dendrimers in solution, the ratio Rg/Rh, depending on the global conformation, varies from 1 (for a Gaussian soft sphere) to 3/5 (for a hard sphere). However, for high-generation dendrimers, this ratio may be less than the limiting value for a hard sphere. To understand the reasons of the low Rg/Rh value (<0.77), we have studied the second-generation peptide dendrimer containing pH-sensitive histidine amino acid residues (Lys-2His dendrimer) using small-angle x-ray (SAXS) and dynamic light scattering (DLS) experiments, as well as molecular dynamics simulations. The Lys-2His dendrimer takes a swollen conformation at pH = 2 and a collapsed 1 at pH = 7. Our results show that the Rg/Rh ratio for the considered dendrimer decreases from ≈3/5 at pH = 2 to 0.5 at pH = 7. We have found that the very low Rg/Rh value is due to (1) the formation of a dense impenetrable core (i.e., the transformation of the dendrimer from a Gaussian soft sphere into a sphere with a dense core) and (2) the presence of a larger number of solvent molecules in the dendrimer corona than in a typical macromolecule. In addition, in this work, we have directly confirmed in the experiments for the first time, the collapse of the Lys-2His dendrimer with increasing pH.

Gram-Scale, One-Pot Synthesis of a Cofacial Porphyrin Bridged by Ortho-xylene as a Scaffold for Dinuclear Architectures.

Herein, we report the reaction between four 1,2-dibromoxylenes and two tetra-3-pyridylporphyrins for the formation of a cofacial porphyrin core spanned by dipyridinium xylene moieties. The metal-free organic nanocage (oNC) was synthesized in one twenty-four h step at a gram-scale with a 91.5% yield. The free base oNC was subsequently metalated with cobalt(II) (Co-oNC), copper(II) (Cu-oNC), and nickel(II) (Ni-oNC) ions to furnish dinuclear complexes that were characterized by mix of mass spectrometry, NMR, EPR, electronic absorption spectroscopy, and for Co-oNC, single-crystal X-ray diffraction. Cofacial cobalt porphyrins are often active as catalysts for the Oxygen Reduction Reaction. Under heterogeneous conditions in water, Co-oNC was 83% selective for the electrocatalytic 4 e-/4 H+ reduction of O2 to H2O, matching homogeneous experiments which revealed consistent selectivity for H2O (88%). This oNC core offers significant advantages over prisms formed by coordination-driven self-assembly: the dipyridnium-xylene coupling can furnish over 1 g of material in a single synthesis and the tethering motif is robust, maintaining a cofacial architecture in acidic and basic solutions. We envision this approach may be generalized to other bis-bromobenzyl building blocks, providing a means to tune metal-metal separation and other structural and electronic properties.

Inflammatory crosstalk impairs phagocytic receptors and aggravates atherosclerosis in clonal hematopoiesis in mice.

Clonal hematopoiesis (CH) increases inflammasome-linked atherosclerosis but the mechanisms by which CH mutant cells transmit inflammatory signals to non-mutant cells are largely unknown. To address this question we transplanted 1.5% Jak2VF bone marrow (BM) cells with 98.5% WT BM cells into hyperlipidemic Ldlr-/- mice. Low allele burden (LAB) mice showed accelerated atherosclerosis with increased features of plaque instability, decreased levels of macrophage phagocytic receptors MERTK and TREM2, and increased neutrophil extracellular traps (NETs). These changes were reversed when Jak2VF BM was transplanted with Il1r1-/- BM. LAB mice with non-cleavable MERTK in WT BM showed improvements in necrotic core and fibrous cap formation and reduced NETs. An agonistic TREM2 antibody (4D9) markedly increased fibrous caps in both control and LAB mice eliminating the difference between groups. Mechanistically, 4D9 increased TREM2+PDGFB+ macrophages and PDGF receptor-α positive fibroblast-like cells in the cap region. TREM2 and PDGFB mRNA levels were positively correlated in human carotid plaques and co-expressed in macrophages. In summary, low frequency Jak2VF mutations promote atherosclerosis via IL-1 signaling from Jak2VF to WT macrophages and neutrophils promoting cleavage of phagocytic receptors and features of plaque instability. Therapeutic approaches that stabilize MERTK or TREM2 could promote plaque stabilization especially in CH- and inflammasome-driven atherosclerosis.

Super broad and protective nanobodies against Sarbecoviruses including SARS-CoV-1 and the divergent SARS-CoV-2 subvariant KP.3.1.1.

The ongoing evolution and immune escape of SARS-CoV-2, alongside the potential threat of SARS-CoV-1 and other sarbecoviruses, underscore the urgent need for effective strategies against their infection and transmission. This study highlights the discovery of nanobodies from immunized alpacas, which demonstrate exceptionally broad and potent neutralizing capabilities against the recently emerged and more divergent SARS-CoV-2 Omicron subvariants including JD.1.1, JN.1, KP.3, KP.3.1.1, as well as SARS-CoV-1 and coronaviruses from bats and pangolins utilizing receptor ACE2. Among these, Tnb04-1 emerges as the most broad and potent, binding to a conserved hydrophobic pocket in the spike's receptor-binding domain, distinct from the ACE2 binding site. This interaction disrupts the formation of a proteinase K-resistant core, crucial for viral-cell fusion. Notably, intranasal administration of Tnb04-1 in Syrian hamsters effectively prevented respiratory infection and transmission of the authentic Omicron XBB.1.5 subvariant. Thus, Thb04-1 holds promise in combating respiratory acquisition and transmission of diverse sarbecoviruses.

Total synthesis of (-)-cylindrocyclophane A facilitated by C-H functionalization.

(-)-Cylindrocyclophane A is a 22-membered C2-symmetric [7.7]paracyclophane that bears bis-resorcinol functionality and six stereocenters. We report a synthetic strategy for (-)-cylindrocyclophane A that uses 10 C-H functionalization reactions, resulting in a streamlined route with high enantioselectivity and efficiency (17 steps). The use of chiral dirhodium tetracarboxylate catalysis enabled the C-H functionalization of primary and secondary positions, which was complemented by palladium-catalyzed C(sp2)-C(sp2) cross-couplings, resulting in the rapid formation of the macrocyclic core and all stereocenters with high regio-, diastereo-, and enantioselectivity. The use of a late-stage palladium-catalyzed fourfold C(sp2)-H acetoxylation installed the bis-resorcinol moieties. This research exemplifies how multilaboratory collaborations can produce substantial modernizations of complex total synthesis endeavors.

Influence of species kinetics on discharge characteristics in oxygen helicon plasma

Abstract Oxygen (O2) helicon plasmas in multiple wave modes were excited by a right-helical antenna with an upper metal endplate at low pressure. Mode transitions were observed at increasing input power or magnetic field, characterized by obvious jumps of plasma parameters. Blue Core appears at high magnetic fields (~700 G) and input powers (~1700 W), with a large radial gradient of plasma density, ion line intensity, and electron temperature. Emission spectra demonstrate that the blue lights originate from O II lines. We found that the intensity ratio of O II to O I of Blue Core in O2 is lower by one order than that in N2 or Ar despite their similar ionization rates and plasma densities in Blue Core area. A high-temperature B-dot probe together with a waveform fitting procedure was used to present the measured oscillating waveforms of m =+1 helicon waves, showing distinct wave structures of different eigenmodes. Cavity mode resonance is suggested to be responsible for the formation of standing waves of discrete eigenmodes. A pressure balance model was developed to estimate the species densities around the central area in different modes, showing massive dissociation of O2 molecules and high density of O atoms locally, so that O2 helicon plasma behaves a species feature of monatomic gas discharge. The obviously low intensity of O II lines compared to O I lines of Blue Core in O2 is related to the quite high excitation threshold of O+ ions (~30 eV) although electron density and temperature are relatively high. The combined effects of dispersed reaction energy distribution, massive molecule dissociation and negative ion creation are considered to be the main causes for requirement of much higher RF power and magnetic field for Blue Core formation in O2 helicon plasma than that in Ar. The calculated radial profile of power deposition and the captured plasma morphology confirm that the dominant central electron heating is the essential reason for the large radial gradients of plasma density and electron temperature which contributes to the serious neutral depletion and Blue Core formation.

Layer-by-Layer Deposition of Hollow TiO2 Spheres with Enhanced Photoelectric Conversion Efficiency for Dye-Sensitized Solar Cell Applications

Fabricating photoanodes with a strong light-scattering effect can improve the photoconversion efficiency of dye-sensitized solar cells (DSSCs). In this work, a facile microwave hydrothermal process was developed to prepare Au@TiO2 core–shell nanostructures, and then the Au core was removed by etching, resulting in hollow TiO2. Morphological characterizations such as field emission scanning and transmission electron microscopy measurements have been used for the successful formation of core–shell and hollow TiO2 nanostructures. Next, we attempted to deposit the different-sized hollow TiO2-based microspheres simultaneously on the surface of small-sized TiO2 nanoparticles-based compact film as light-scattering layers via electrophoretic deposition. The deposited hollow TiO2 microspheres constitute bi- and tri-layers that not only improve the light-harvesting properties but also speed up the photogenerated charge transfer. Compared to commercial TiO2 compact film (4.75%), the resulting bi-layer and tri-layered films-based DSSCs displayed power conversion efficiencies of 6.33% and 8.08%, respectively. It is revealed that the deposited bi- and tri-layered films can enhance the light absorption ability via multiple photon reflection. This work validates a novel and controllable strategy to develop light-scattering layers with increased light-harvesting properties for highly efficient dye-sensitized solar cells.

Bursty Star Formation in Dwarfs is Sensitive to Numerical Choices in Supernova Feedback Models

Simulations of galaxy formation are mostly unable to resolve the energy-conserving phase of individual supernova events, having to resort to subgrid models to distribute the energy and momentum resulting from stellar feedback. However, the properties of these simulated galaxies, including the morphology, stellar mass formed, and the burstiness of the star formation history, are highly sensitive to the numerical choices adopted in these subgrid models. Using the SMUGGLE stellar feedback model, we carry out idealized simulations of an M vir ∼ 1010 M ⊙ dwarf galaxy, a regime where most simulation codes predict significant burstiness in star formation, resulting in strong gas flows that lead to the formation of dark matter cores. We find that by varying only the directional distribution of momentum imparted from supernovae to the surrounding gas, while holding the total momentum per supernova constant, bursty star formation may be amplified or completely suppressed, and the total stellar mass formed can vary by as much as a factor of ∼3. In particular, when momentum is primarily directed perpendicular to the gas disk, less bursty and lower overall star formation rates result, yielding less gas turbulence, more disky morphologies, and a retention of cuspy dark matter density profiles. An improved understanding of the nonlinear coupling of stellar feedback into inhomogeneous gaseous media is thus needed to make robust predictions for stellar morphologies and dark matter core formation in dwarfs independent of uncertain numerical choices in the baryonic treatment.

Fabrication of LTA Zeolite Core and UiO-66 Shell Structures via Surface Zeta Potential Modulation and Sequential Seeded Growth for Zeolite/Polymer Composite Membranes

Zeolite-based polymer composites have garnered significant attention for their applications in separation, catalysis, and energy storage, owing to the unique properties of zeolites. The development of core–shell structures provides a promising strategy to enhance these properties, enabling the fine-tuning of zeolite characteristics within composite films. In this study, we present an innovative approach that leverages surface zeta potential differences to facilitate the growth of an organophilic metal–organic framework (MOF) on hydrophilic zeolite surfaces. Specifically, UiO-66 was successfully attached and grown on Linde Type A (LTA) zeolite particles, resulting in the formation of a robust core–shell structure (LTA@UiO-66). This core–shell architecture significantly minimized interfacial voids when embedded into a polyimide (PI, Matrimid® 5218) matrix, yielding composite films (LTA@UiO-66/PI) with superior mechanical integrity and enhanced gas-separation performance. The LTA@UiO-66/PI films demonstrated remarkable ideal selectivity for O2/N2 (10.7) and CO2/CH4 (47), outperforming traditional LTA/PI composites. These enhancements are attributed to the synergistic effects between the LTA core and the UiO-66 shell, which preserve the molecular sieving capability of the zeolite while ensuring strong adhesion and a void-free interface with the polymer matrix. The findings underscore the significant potential of zeolite-based core–shell structures in advancing industrial applications, particularly in the domains of sustainable gas separation and purification technologies.

Hf–W isotope systematics of bulk chondrites: Implications for early Solar System evolution

The short-lived 182Hf–182W system is widely used for constraining the chronology of the early Solar System, including the timing of the formation, thermal evolution, and differentiation of planetary bodies. Utilizing the full potential of the Hf–W system requires knowledge of the Hf/W ratio and W isotopic composition of primitive chondritic material. However, metal-silicate heterogeneity among chondritic samples can complicate accurately determining the Hf–W systematics of bulk chondrite parent bodies. Moreover, interpreting Hf–W data for chondrites may be complicated by potential nucleosynthetic W isotope anomalies. To this end, we report Hf/W ratios and W isotope compositions for bulk ordinary and enstatite chondrites, as well as the first such data for Rumuruti chondrites. We find that ordinary and Rumuruti chondrites show no resolvable nucleosynthetic anomalies, whereas resolved ε183W (i.e., 0.01 % deviation in 183W/184W from terrestrial standard) excesses in individual enstatite chondrites suggest the presence of nucleosynthetic W isotope anomalies in bulk meteorite samples originating in the inner Solar System. These anomalies necessitate corrections when accurately quantifying radiogenic 182W variations. Furthermore, several ordinary chondrites deviate in Hf/W ratios and W composition from the parent body compositions previously obtained from internal 182Hf–182W isochrons, indicating variations in the abundance of metal across different chondrite samples. Similarly, the Hf–W systematics of some enstatite chondrites also deviate from the parent body values, which can be attributed to the heterogeneous distribution of Hf carrier phases. The new observations highlight the challenges in obtaining Hf-W data that are representative of the chondrite parent bodies from individual chondrites, especially from metal-rich samples. By contrast, Rumuruti chondrites of variable petrologic types exhibit uniform Hf/W and 182W/184W ratios, suggesting that these samples are representative of their parent body. Whereas their Hf/W ratio is similar to that of carbonaceous chondrites, their W isotope composition is less radiogenic. This indicates that the Rumuruti precursor reservoir most likely had a significantly lower Hf/W ratio than the ratio measured in Rumuruti chondrites today. These findings underscore the importance of understanding the likely variations in Hf-W isotope systematics of iron meteorite parent bodies for accurately determining the timing of core formation.

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts.

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/Al2O3) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/Al2O3 catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. The structure-activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

Hierarchical core-shell ZIF-11@ZIF-8 composite nanocatalyst for high-yield simultaneous transesterification-esterifications of sunflower oil to produce biodiesel

Decreasing the mass transfer resistance is a promising technique to prepare an efficient catalyst for improving biomass macromolecules conversion in biodiesel production. In this study, hierarchical core–shell composite nanocatalysts were prepared through a solvothermal technique using zeolitic imidazolate framework-8 (ZIF-8) and ZIF-11 metal–organic frameworks (MOFs). The nanocatalysts were characterized by XRD, FT-IR, BET, FE-SEM, EDS, XPS, TEM, NH3-TPD, and CO2-TPD analyses. The results showed high crystallinity, high surface area (1446.86 m2/g), high pore volume (0.65 cm3 g−1), and mesoscale pore size (2.37 nm). Furthermore, TEM images confirmed the formation of core–shell structure for the composites. The catalytic activity was evaluated in the transesterification of sunflower oil at different operating conditions. The highest biodiesel yield (96.4 %) and full free fatty acid (FFA) conversion were obtained over the ZIF-11@ZIF-8 nanocatalyst at the optimum operating conditions: 120 °C, catalyst concentration of 8 wt%, methanol to oil ratio of 40:1, and 10 h. The ZIF-11@ZIF-8 nanocatalyst showed high thermal and chemical stability after several sequence cycles, leading to high reusability.

Unravelling the Complexity of Amyloid Peptide Core Interfaces.

Amyloids, large intermolecular sandwiched β-sheet structures, underlie several protein misfolding diseases but have also been shown to have functional roles and can be a basis for designing smart and responsive nanomaterials. Short segments of proteins, called aggregation-prone regions (APRs), have been identified that nucleate amyloid formation. Here we present the database of 173 APR crystal structures currently available in the PDB, and a tool, ACW, for analyzing their topologies and the 267 inter-β-sheet interfaces of zipper regions assigned in these structures. We defined a new descriptor of zipper interfaces, the surface detail index (SDi), which quantifies the intertwining between the side chains of both β-sheets of the zipper, an important factor for the molecular recognition and self-assembly of these mesostructures. This allowed a comparative analysis of the zipper interfaces and identification of 6 clusters with different intertwining, steric fit, and size characteristics using three complementary descriptors, SDi, shape complementarity, and buried surface area. 60% of the APR structures are formed by parallel β-sheets, of which 52% belong to the topological class 1. This could be explained by the better fit and a deeper entanglement of the zipper regions of the parallel structures than of the antiparallel structures, as the analysis showed that both their shape complementarity (0.79 vs 0.70) and SDi (1.53 vs 1.32) were higher. The higher abundance of certain residues (Asn and Gln in parallel and Leu and Ala in antiparallel β-sheets) can be explained by their ability to form different ladder-like secondary interaction patterns within β-sheets. Analogous to the hierarchy of protein structure, we interpreted the primary, secondary, tertiary, and quaternary structure levels of APRs revealing different characteristics of the zipper regions for both parallel and antiparallel β-sheet structures, which may provide clues to the structural conditions of amyloid core formation and the rational design of amyloid polymorphs.

Diesel exhaust particles activate macrophages and IRF5 expression in atherosclerosis

Abstract Introduction Over 20% of global deaths related to cardiovascular disease have been attributed in part to air pollution, particularly fine particulate matter (PM2.5) (1). In highly trafficked urban areas, smaller ultrafine diesel exhaust particles (DEP) represent a significant proportion of PM2.5. DEP is associated with the progression of atherosclerosis and increased plaque susceptibility to rupture (2). We have previously shown that interferon regulatory factor 5 (IRF5) has a key role in necrotic core formation, a distinguishing feature of vulnerable atherosclerotic plaques, by rendering macrophages defective at efferocytosis (3). Pronounced elevation of IRF5 is also seen in symptomatic carotid plaques, particularly in the rupture-prone shoulder regions (4). Purpose We examined the effect of DEP on macrophage phenotype and IRF5 expression in atherosclerosis. Methods Bone marrow-derived macrophages (BMDMs) from C57BL/6 mice, differentiated with GM-CSF (to mimic inflammatory macrophages) or M-CSF (mimicking homeostatic resident macrophages) were incubated with PBS or DEP (10 µg/mL) in vitro for 18 hours. Expression of inflammatory cytokines (IL-6, IL-12α), macrophage polarisation markers CD11c (itgax, inflammatory) and CD206 (mrc1, resident anti-inflammatory) and IRF5 was quantified by real-time PCR. In addition, high fat-fed ApoE-/- mice were exposed to saline or DEP (35 µL at 1 mg/mL) twice weekly for 5 weeks by pulmonary administration. The pan-macrophage marker CD64, CD206 and IRF5 were quantified in paraffin-embedded sections of brachiocephalic artery lesions by immunohistochemistry. Results In M-CSF-differentiated murine macrophages incubated with DEP, significant fold increases in gene expression (relative to PBS control) were observed: IRF5 (1.4-fold), IL-6 (31.5-fold) and IL-12α (5.8-fold) while CD206 (0.8-fold) decreased (Figure 1a, n = 5, p&amp;lt;0.05, two-tailed paired t-tests). CD11c expression was unchanged. No statistically significant differences were detected in GM-CSF-differentiated macrophages. In the brachiocephalic arteries of DEP-exposed ApoE-/- mice we observed increases in CD64+ macrophages (28.2±7.4 vs 15.5±5.6) and IRF5 (16.6±3.6 vs 10.1±3.4) expression, while CD206 expression decreased (4.1±0.9 vs 11.0±1.2) in comparison to saline-exposed mice (Figure 1b mean±SD, n = 5, p&amp;lt;0.05, two-tailed unpaired t-tests, data expressed as % of intima area). Conclusion DEP promotes CD64+ macrophages and IRF5 expression in murine atherosclerosis, while inflammation and IRF5 is induced in vitro, but only in M-CSF-differentiated murine BMDMs. This suggests that DEP has no impact on inflammatory macrophages but could switch homeostatic resident macrophages to a more inflammatory phenotype via the activation of IRF5. Therefore, IRF5 is a promising candidate for further investigation into the initial macrophage response to inhaled particles that leads to the exacerbation of vascular disease.

Dynamic culture of cerebral organoids using a pillar/perfusion plate for the assessment of developmental neurotoxicity

Despite the potential toxicity of commercial chemicals to the development of the nervous system (known as developmental neurotoxicity or DNT), conventionalin vitrocell models have primarily been employed for the assessment of acute neuronal toxicity. On the other hand, animal models used for the assessment of DNT are not physiologically relevant due to the heterogenic difference between humans and animals. In addition, animal models are low-throughput, time-consuming, expensive, and ethically questionable. Recently, human brain organoids have emerged as a promising alternative to assess the detrimental effects of chemicals on the developing brain. However, conventional organoid culture systems have several technical limitations including low throughput, lack of reproducibility, insufficient maturity of organoids, and the formation of the necrotic core due to limited diffusion of nutrients and oxygen. To address these issues and establish predictive DNT models, cerebral organoids were differentiated in a dynamic condition in a unique pillar/perfusion plate, which were exposed to test compounds to evaluate DNT potential. The pillar/perfusion plate facilitated uniform, dynamic culture of cerebral organoids with improved proliferation and maturity by rapid, bidirectional flow generated on a digital rocker. Day 9 cerebral organoids in the pillar/perfusion plate were exposed to ascorbic acid (DNT negative) and methylmercury (DNT positive) in a dynamic condition for 1 and 3 weeks, and changes in organoid morphology and neural gene expression were measured to determine DNT potential. As expected, ascorbic acid did not induce any changes in organoid morphology and neural gene expression. However, exposure of day 9 cerebral organoids to methylmercury resulted in significant changes in organoid morphology and neural gene expression. Interestingly, methylmercury did not induce adverse changes in cerebral organoids in a static condition, thus highlighting the importance of dynamic organoid culture in DNT assessment.

The supermassive black hole merger-driven evolution of high-redshift red nuggets into present-day cored early-type galaxies

ABSTRACT Very compact ($R_\mathrm{e}\lesssim 1$ kpc) massive quiescent galaxies (red nuggets) are more abundant in the high-redshift Universe ($z\sim 2$–3) than today. Their size evolution can be explained by collisionless dynamical processes in galaxy mergers which, however, fail to reproduce the diffuse low-density central cores in the local massive early-type galaxies (ETGs). We use sequences of major and minor merger N-body simulations starting with compact spherical and disc-like progenitor models to investigate the impact of supermassive black holes (SMBHs) on the evolution of the galaxies. With the ketju code we accurately follow the collisional interaction of the SMBHs with the nearby stellar population and the collisionless evolution of the galaxies and their dark matter haloes. We show that only models including SMBHs can simultaneously explain the formation of low-density cores up to sizes of $R_\mathrm{b} \sim 1.3$ kpc with mass deficits in the observed range and the rapid half-mass size evolution. In addition, the orbital structure in the core region (tangentially biased orbits) is consistent with observation-based results for local cored ETGs. The displacement of stars by the SMBHs boost the half-mass size evolution by up to a factor of 2 and even fast rotating progenitors (compact quiescent discs) lose their rotational support after 6–8 mergers. We conclude that the presence of SMBHs is required for merger-driven evolution models of high-redshift red nuggets into local ETGs.

Accretion and Core Formation of Earth-like Planets: Insights from Metal–Silicate Partitioning of Siderophile and Volatile Elements

The origin of volatile elements, the timing of their accretion and their distribution during Earth’s differentiation are fundamental aspects of Earth’s early evolution. Here, we present the result of a newly developed accretion and core formation model, which features the results of high P–T metal–silicate partitioning experiments. The model includes well-studied reference elements (Fe, Ni, Ca, Al, Mg, Si) as well as trace elements (V, Ga, Ag, Au, S) covering a wide range from refractory to volatile behavior. The accretion model simulates the different steps of planet formation, such as the effects of continuous, heterogenous core formation at high P–T, the effect of the Moon-forming giant impact and the addition of matter after the core formation was completed, the so-called “late veneer”. To explore the “core formation signature” of the volatile depletion patterns and the quantitative influence of a late veneer, we modeled planets that would have formed from known materials, such as CI, CM, CV, CO, EH and EL meteorites, and from a hypothetical volatile depleted material, CI*. Some of the resulting planets are Earth-like in key properties, such as overall core size, major element composition, oxygen fugacity and trace element composition. The model predicts the chemical signatures of the main planetary reservoirs, the metallic core and bulk silicate planet (BSP) of the modeled planets, which we compare with the chemical signature of Earth derived previously from core formation models and mass balance-based approaches. We show that planets accreted from volatile depleted carbonaceous chondrites (CM, CV, CO and CI*) are closest in terms of major element (Si, Mg, Fe, Ca, Al, Ni) and also siderophile volatile element (Ge, Ga, Au) concentrations to the components from which Earth accreted. Chalcophile volatile elements (S, Ag), instead, require an additional process to lower their concentrations in the BSP to Earth-like concentrations, perhaps the late segregation of a sulfide melt.

Formation of core–shell structures and viscous fingering in cellulose beads regenerated from [DBNH][OAc]/DMSO

AbstractSuperbase Ionic Liquids (SBILs) are efficient direct-dissolution solvents for cellulose and have found applications such as manufacturing of man-made textile fibers. In this study cellulose beads were prepared from microcrystalline cellulose dissolved in a mixture of SBIL 1,5-diazabicyclo[4.3.0]non-5-enium acetate with dimethyl sulfoxide, [DBNH][OAc]/DMSO, by drop-wise regeneration using water as an antisolvent. This resulted in cellulose regeneration by spinodal decomposition phase separation. The cross-sections of freeze-dried beads were thoroughly investigated using SEM, revealing a complex internal bead structure. Special attention was paid to structures resulting from the inwards moving regeneration front, where the solvent and antisolvent interdiffuse in opposite directions. The phase boundary at the regeneration front showed evidence of Saffman–Taylor instability, i.e., viscous fingering. Altering the diffusion environment surrounding the bead during regeneration resulted in nested layers of cores and shells. The number and placement of the core–shell separations was regulated by the number of transfers between two antisolvent baths and the duration of alternating periods of fast and slow interdiffusion of water and [DBNH][OAc]/DMSO through the bead perimeter. Graphical abstract

GEOCHEMISTRY OF GROUNDWATERS AND SURFACE WATERS, AND GROUND ICE OF THE OKA PLATEAU, EASTERN SAYAN (RUSSIA)

The study area is located in the Eastern Sayan hydrogeological folded area. The objects of the study were groundwaters, surface waters and ground ice in the Sentsa River basin on the Oka Plateau. Cold and thermal groundwaters are associated with Proterozoic and Paleozoic metamorphic and igneous rocks. Their discharge as springs occurs in the river valleys along fault zones. Ground ice was studied in mineral frost mounds (lithalsas) composed of clays, clayey silts and silts of lacustrine-alluvial and fluvioglacial genesis. It has been established that thermal and cold groundwaters have HCO3 Ca-Na compositions, river and lake waters, as a rule, have HCO3 Ca-Na compositions, and ground ice melts – HCO3, SO4-HCO3 and NH4-HCO3 Ca. Thermal waters are largely enriched in Li, Be, B, Si, Mn, Ga, Ge, Se, As, Br, Rb, Sr, Cs, Ba and all REE relative to river and rain waters, and have the highest values of trace elements enrichment factor (EFREE). The latter shows that atmospheric precipitation participates in the formation of the composition of groundwaters (cold and thermal) and surface waters. The specificity of the geochemistry of ground ice is determined by the composition of precipitation, the injection of ice-forming groundwater from taliks, the interaction in the water-rock system, and the presence of organic matter in unconsolidated sediments. The participation of river water and groundwater in the formation of the frost mound ice core is also evidenced by similar values of stable isotopes (δ18O, δD) in surface water, groundwater and ground ice. The 3He/4He ratio points to a possible influx of mantle helium into thermal waters, and δ13С points to the magmatic and thermometamorphic mechanisms of carbon dioxide accumulation in thermal waters. The 87Sr/86Sr ratio in travertines indicates a significant contribution of intrusive rocks to the formation of fluid composition.

Assembling phthalaldehyde and o-aminochalcones by Pd(II) catalyzed tandem reaction for synthesizing isoindoloindonole fluorophores

One-pot synthesis of isoindoloindonoles having various auxochrome, from easily available starting materials phthalaldehyde and o-aminochalcone, involving palladium(II) acetate catalysis in acetic acid is reported. A mechanism based on the formation of 2-aryl-2H-isoindol-1-ol (22) intermediate is proposed for the formation of the tetracyclic core of isoindoloindonoles. The possible intramolecular cyclization via the direct participation of the carbonyl vs the adjacent αβ-conjugated double bond was evaluated. Thus, a detailed study on how the presence of electronically different groups at the β position of chalcones affects the outcome of the cyclization reaction and the photophysical properties of the resulting isoindoloindolones is presented here. Furthermore, the core structure was determined using NMR, mass and single-crystal X-ray diffraction analysis.