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The archaeal Asgard superphylum currently stands as the most promising prokaryotic candidate, from which eukaryotic cells emerged. This unique superphylum encodes for eukaryotic signature proteins (ESP) that could shed light on the origin of eukaryotes, but the properties and function of these proteins is largely unresolved. Here, we set to understand the function of an Asgard archaeal protein family, namely the ESCRT machinery, that is conserved across all domains of life and executes basic cellular eukaryotic functions, including membrane constriction during cell division. We find that ESCRT proteins encoded in Loki archaea, express in mammalian and yeast cells, and that the Loki ESCRT-III protein, CHMP4-7, resides in the eukaryotic nucleus in both organisms. Moreover, Loki ESCRT-III proteins associated with chromatin, recruited their AAA-ATPase VPS4 counterpart to organize in discrete foci in the mammalian nucleus, and directly bind DNA. The human ESCRT-III protein, CHMP1B, exhibited similar nuclear properties and recruited both human and Asgard VPS4s to nuclear foci, indicating interspecies interactions. Mutation analysis revealed a role for the N terminal region of ESCRT-III in mediating these phenotypes in both human and Asgard ESCRTs. These findings suggest that ESCRT proteins hold chromatin binding properties that were highly preserved through the billion years of evolution separating Asgard archaea and humans. The conserved chromatin binding properties of the ESCRT membrane remodeling machinery, reported here, may have important implications for the origin of eukaryogenesis.

In a lithium–sulfur battery (LSB) discharge process, elemental sulfur is reduced to Li2S via a multi-step process. The soluble lithium-polysulfide (PS) (Li2Sn) intermediate species then diffuses th...

Catalyst poisoning is a prominent issue, reducing the lifetime of catalysts and increasing the costs of the processes that rely on them. The electrocatalysts that enable green energy conversion and storage, such as proton exchange membrane fuel cells and hydrogen bromine redox flow batteries, also suffer from this issue, hindering their utilization. Current solutions to protect electrocatalysts from harmful species fall short of effective selectivity without inhibiting the required reactions. This article describes the protection of a standard 50% Pt/C catalyst with a V2O5 coating through atomic layer deposition (ALD). The ALD selectively deposited V2O5 on the Pt, which enhanced hydrogen transport to the Pt surface and resulted in a higher mass activity in alkaline electrolytes. Cyclic voltammetry and X-ray photoelectron spectroscopy showed that the Pt was protected by the coating in the HBr/Br2 electrolyte which dissolved the uncoated 50% Pt/C in under 3 min.

Rechargeable metal–sulfur batteries (RMSBs) represent one of the most attractive electrochemical systems in terms of energy density and cost. In most of the proposed systems, the anode side is metallic and the cathode side is elemental sulfur impregnated in a porous matrix. Despite the relatively low voltage of these systems, they attract a lot of attention and are considered to be very promising as next-generation batteries for the following reasons: (1) utilization of active metal anodes enables a leap in specific energy due to the high capacity of metal anodes in comparison to intercalation compounds, (2) sulfur as a cathode exhibits high theoretical specific capacity (1675 mAh/g), and (3) system components make RMSBs low-cost, less toxic batteries. Nevertheless, the high reactivity of metallic anodes (e.g., Li, Na, Mg, and Al) and the solubility of sulfur species in the electrolyte render these batteries unstable and hinder their practical realization. In this Perspective, we focus on rechargeable sul...

Metal-support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1-5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide-metal interface. However, catalytically active sites are not necessarily restricted to the interface but reside as well on the Au surface. Uncovering the interconnection between reactive sites located at the interface and those situated at the metal surface is of crucial importance for understanding the reaction mechanism on Au nanoparticles. Herein, high-spatial-resolution IR nanospectroscopy measurements were conducted to map the localized reactivity in hydrogenation reactions on oxide-supported Au particles while using nitro-functionalized ligands as probes molecules. Comparative analysis of the reactivity pattern on single particles supported on various oxides revealed that oxide-dependent reactivity enhancement was not limited to the oxide-metal interface but was detected throughout the Au particle, leading to site-independent reactivity. These results indicate that reactive Au sites on both the oxide-metal interface and metal surface can activate the nitro groups toward hydrogenation reactions. The observed influence of oxide support (TiO2 > SiO2 > Al2O3) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide-metal interface, followed by highly efficient intraparticle hydrogen atom diffusion to the interior parts of the Au particle. In contrast to Au particles, the oxide-metal interface had only a minor impact on the reactivity of supported Pt particles in which hydrogen dissociation and nitro group reduction were effectively activated on Pt sites. Single-particle measurements provided insights into the relative reactivity pattern of oxide-supported Au particles, revealing that the less-reactive Au metal sites can activate hydrogenation reactions in the presence of hydrogen atoms that diffuse from the Au/oxide boundary.

We analyzed the effect of nickel overlayers positioned in close proximity (bridges) or in contact (stencils) with the catalytic layer on the growth of vertically aligned carbon nanotubes (VACNTs) using thermal chemical vapor deposition (CVD). We studied the physical–chemical mechanisms, namely, the interaction of the overlayer with the gases and with the catalyst. We demonstrate that nickel inhibits CNT growth by adsorbing carbon to form graphene and by interacting with the gas precursors, leading to their modification into species that do not nucleate and grow CNTs. We demonstrate that the effect of the nickel bridge extends to the length of its boundary layer. We tested overlayer patterns and showed that the patterns were replicated during CNT growth. This facile method is a valid alternative to pattern CNT forests without the need for complex lithography and lift-off of the catalyst in applications where lithographic precision is not required.

One of the many challenges in the study of chiral nanosurfaces and nanofilms is the design of accurate and controlled nanoscale films with enantioselective activity. Controlled design of chiral nanofilms creates the opportunity to develop chiral materials with nanostructured architecture. Molecular layer deposition (MLD) is an advanced surface-engineering strategy for the preparation of hybrid inorganic-organic thin films, with a desired embedded property; in our study this is chirality. Previous attempts to grow enantioselective thin films were mostly focused on self-assembled monolayers or template-assisted synthesis, followed by removal of the chiral template. Here, we report a method to prepare chiral hybrid inorganic-organic nanoscale thin films with controlled thickness and impressive enantioselective properties. We present the use of an MLD reactor for sequenced vapor deposition to produce enantioselective thin films, by embedding the chirality of chiral building blocks into thin films. The prepared thin films demonstrate enantioselectivity of ∼20% and enantiomeric excess of up to 50%. We show that our controlled synthesis of chiral thin films generates opportunities for enantioselective coatings over various templates and 3D membranes.

Using a system of multi-zone thermal chemical vapor deposition (CVD) furnaces in parallel and in series, we performed differential preheating of the incoming gases to independently control water vapor formation (from oxygen and hydrogen) and hydrocarbon decomposition to grow vertically aligned multi-wall carbon nanotube (MWCNT) carpets. We identified specific process parameter sweet spots for water vapor formation and for hydrocarbon decomposition that led to over three times taller CNT carpets compared to the reference process. For instance, we performed a kinetic study that showed that additional external preheating of oxygen and hydrogen to form water vapor significantly extended catalyst life, leading to a terminal height approaching 5 mm, while external preheating of the hydrocarbon precursors dramatically hindered CNT growth at high thermal doses. Using gas chromatography – mass spectrometry, we correlated specific carbon species resulting from ethylene decomposition from specific process points to reveal which species favored and which hindered CNT growth. We identified that hydrocarbons composed of one benzene ring connected to different substituents favored CNT growth while hydrocarbons composed of multiple aromatic rings hindered CNT growth. This study can further our understanding of CNT growth mechanisms and help designing complex CVD systems for more efficient synthesis of CNTs.

We show a simple technique to grow patterned carbon nanotube (CNT) forests by annealing the catalytic surface using copper patterns (as stencil or bridge) prior to, or during, CNT growth. We demonstrate that copper diffused into the iron catalyst and deactivated it, thus preventing CNT growth on the areas where the copper was present. This technique is a promising and simple way to pattern CNT forests since it does not require the usual lithography and lift-off of the catalyst. This catalyst deactivating overlayer principle can be extended to pattern other 1D nanostructures such as carbon nanofibers or nanowires and 2D nanostructures such as graphene or transition metal dichalcogenides using chemical vapor deposition (CVD).

The number of patients suffering from inflammatory bowel disease (IBD) is increasing worldwide. The development of noninvasive tests that are rapid, sensitive, specific, and simple would allow preventing patient discomfort, delay in diagnosis, and the follow-up of the status of the disease. Herein, we show the interest of vertically aligned nitrogen-doped carbon nanotube (VA-NCNT) electrodes for the required sensitive electrochemical detection of lysozyme in serum, a protein that is up-regulated in IBD. To achieve selective lysozyme detection, biotinylated lysozyme aptamers were covalently immobilized onto the VA-NCNTs. Detection of lysozyme in serum was achieved by measuring the decrease in the peak current of the Fe(CN)6(3-/4-) redox couple by differential pulse voltammetry upon addition of the analyte. We achieved a detection limit as low as 100 fM with a linear range up to 7 pM, in line with the required demands for the determination of lysozyme level in patients suffering from IBD. We attained the sensitive detection of biomarkers in clinical samples of healthy patients and individuals suffering from IBD and compared the results to a classical turbidimetric assay. The results clearly indicate that the newly developed sensor allows for a reliable and efficient analysis of lysozyme in serum.

Rechargeable magnesium batteries (RMBs) have attracted a lot of attention in recent decades due to the theoretical properties of these systems in terms of energy density, safety, and price. Nevertheless, to date, fully rechargeable magnesium battery prototypes with sufficient longevity and reversibility were realized only with low voltage and low capacity intercalation cathode materials based on Cheverel phases. The community is therefore actively looking for high-capacity cathodes that can work with metallic magnesium anodes in viable RMB systems. One of the most promising cathode materials, in terms of very high theoretical specific capacity, is, naturally, sulfur. A number of recent works studied the electrochemical performances of rechargeable sulfur cathodes in RMB, with success to some extent on the cathode side. Nevertheless, as known from the lithium-sulfur rechargeable battery systems, the formation of soluble polysulfides during discharge affects strongly the behavior of the anode side. In this article and the work it describes, we focus on soluble polysulfides impact on Mg-S electrochemichal systems. We carefully designed herein conditions that mimic the Mg-S battery prototypes containing balanced Mg and elemental sulfur electrodes. Under these conditions, we extensively studied the Mg anode behavior. The study shows that when elemental sulfur cathodes are discharged in the Mg-S cells containing electrolyte solutions in which Mg anodes behave reversibly, the polysulfide species thus formed migrate to the anode and eventually fully passivate it by the formation of very stable surface layers. The work involved electrochemical, spectroscopic, and microscopic studies. The present study clearly shows that to realize practical rechargeable Mg-S batteries, the transport of any sulfide moieties from the sulfur cathode to the magnesium anode has to be completely avoided. Such a condition is mandatory for the operation of secondary Mg-S batteries.

The oxidation level and properties of reduced graphene oxides (rGOs) were fine-tuned using temperature-programmed reductive annealing. rGOs were annealed at different temperatures (from 500 to 1000 °C) in hydrogen to modulate their oxidation levels. The surface of the rGOs was fully characterized using electron paramagnetic resonance backed by Raman, X-ray diffraction, and chemical analysis measurements. These experiments were used to study the changes in the surface of the rGO, its surface functionalities, and its defects as a function of the reduction temperature. In addition, electrochemical measurements to quantify the oxidation level of the rGOs offer a simple tool to correlate the properties of rGOs with their structure. Finally, we explored the effect of different levels of reduction on conductivity, capacitance, and surface reactivity. This research offers simple methodological techniques and routes to control and characterize the oxidation level of bulk quantities of rGO.