Insight into Fluoride Additives to Enhance Ammonia Production from Lithium-Mediated Electrochemical Nitrogen Reduction Reaction.

Demands for green ammonia production increase due to its application as a proton carrier, and recent achievements in electrochemical Li-mediated nitrogen reduction reactions (Li-NRRs) show promising reliability. Here, it is demonstrated that F-containing additives in the electrolyte improve ammonia production by modulating the solid electrolyte interphase (SEI). It is suggested that the anionic additives with low lowest unoccupied molecular orbital levels enhance efficiency by contributing to the formation of a conductive SEI incorporated with LiF. Specifically, as little as 0.3 wt.% of BF4 - additive to the electrolyte, the Faradaic efficiency (FE) for ammonia production is enhanced by over 15% compared to an additive-free electrolyte, achieving a high yield of 161 ± 3 nmol s-1 cm-2. The BF4 - additive exhibits advantages, with decreased overpotential and improved FE, compared to its use as the bulk electrolyte. The observation of the Li3N upper layer implies that active Li-NRR catalytic cycles are occurring on the outermost SEI, and density functional theory simulations propose that an SEI incorporated with LiF facilitates energy profiles for the protonation by adjusting the binding energies of the intermediates compared to bare copper. This study unlocks the potential of additives and offers insights into the SEIs for efficient Li-NRRs.

Energy-Efficient and Self-Powered Green Ammonia Synthesis by Electrochemical Nitrate Reduction Combined with Hydrazine Oxidation.

To achieve the global goal of carbon neutrality, recently, emphasis has been placed on developing green ammonia production method to replace the Haber-Bosch process. Nitrate reduction reaction (NO3 RR) has received considerable attention, especially for electrochemically producing ammonia from nitrate and simultaneously purifying wastewater. This study first demonstrates that the combination of NO3 RR with hydrazine oxidation reaction (HzOR) is an energy efficient green ammonia production method, which overcomes the sluggish water oxidation limitation. Tungsten phosphide (WP) nanowires (NWs) are prepared as cathode NO3 RR electrocatalysts, which exhibit a high Faradaic efficiency in both neutral (≈93%) and alkaline (≈85%) media. Furthermore, they show a high bifunctional activity in anodic reactions and exhibit a low potential 0.024 V for generating a current density of 10 mA cm-2 in HzOR. The overall NO3 RR-HzOR required an impressively low potential of 0.24 V for generating a current density of 10 mA cm-2 ; this potential is much lower than those required for NO3 RR-OER (1.53 V) and NO3 RR-UOR (1.31 V). A self-powered ammonia production system, prepared by assembling an NO3 RR-HzOR with a perovskite solar cell, displays a high ammonia production rate of 1.44 mg cm-2  h-1 . A single PV cell provides enough driving voltage in the PV-EC due to low required potential. This system facilitates unassisted green ammonia synthesis with a low energy consumption and also allows upcycling of wastewater to produce useful fuel.

Protocol for in vitro co-culture assay for rapid expansion of human T cell acute lymphoblastic leukemia.

T cell acute lymphoblastic leukemia (T-ALL) is a rare but aggressive hematological cancer that occurs primarily in children and adolescents. Here, we present a protocol for in vitro co-culture assay that enables robust expansion of primary T-ALL cells. We describe steps for seeding T-ALL and stromal cells in 3D organoids and subsequent flow analysis to capture the T-ALL cell growth for long-term culture. This protocol provides a valuable platform for in vitro functional studies and drug screenings using patient-derived cells. For complete details on the use and execution of this protocol, please refer to Rivera et al.1.

Photolabile Protecting Groups Based on the Excited State Meta Effect: Development and Application.

This review focuses on utilization of the excited state meta effect (ESME) in the development of photolabile protecting groups (PPGs). Structurally simple ESME-based PPGs for release of various functional groups (such as carbonyl, hydroxyl, carboxyl, amino and thiol groups) are discussed. Examples that demonstrate the appealing advantages of these new PPGs are provided, including their efficient release of "poor" leaving groups such as hydroxyl or amino group directly instead of in their respective carbonate or carbamate form. Applications of these PPGs in synthesis, release of biologically important molecules, materials science and biomedical engineering are also described.

Proton-coupled electron transfer reactivities of electronically divergent heme superoxide intermediates: a kinetic, thermodynamic, and theoretical study.

Heme superoxides are one of the most versatile metallo-intermediates in biology, and they mediate a vast variety of oxidation and oxygenation reactions involving O2(g). Overall proton-coupled electron transfer (PCET) processes they facilitate may proceed via several different mechanistic pathways, attributes of which are not yet fully understood. Herein we present a detailed investigation into concerted PCET events of a series of geometrically similar, but electronically disparate synthetic heme superoxide mimics, where unprecedented, PCET feasibility-determining electronic effects of the heme center have been identified. These electronic factors firmly modulate both thermodynamic and kinetic parameters that are central to PCET, as supported by our experimental and theoretical observations. Consistently, the most electron-deficient superoxide adduct shows the strongest driving force for PCET, whereas the most electron-rich system remains unreactive. The pivotal role of these findings in understanding significant heme systems in biology, as well as in alternative energy applications is also discussed.

Complete mitogenome sequences of a Korean spine loach, Iksookimia koreensis (Kim, 1975).

Here, we present the complete mitogenome sequences from a Korean spine loach (Iksookimia koreensis Kim 1975), an endemic species of Korea. The total length of mitogenome was 16 563 bp, consisting of 13 protein-coding genes, 22 tRNA genes, 2 rRNA genes and one control region (D-loop). Except for ND6 and eight tRNA genes, all of the other mitochondrial genes were encoded on the heavy strand. The control region harbored conserved sequence blocks (CSB-D, E, F, CSB-1, CBS-2 and CBS-3) and TA-nucleotide microsatellite repeats in its 3' end. Our complete mitogenomes will be valuable resources for phylogeny, genetics and conservation of the genus Iksookimia.

The complete chloroplast genome of Aconitum austrokoreense Koidz. (Ranunculaceae), an endangered endemic species in Korea.

We determined the complete chloroplast genome sequences of Aconitum austrokoreense Koidz., an endangered endemic species in Korea. The chloroplast DNA is 155,682 bp in length and encodes 37 tRNAs, 8 rRNAs, and 86 protein-coding genes. Phylogenetic analysis and sequence comparison of protein-coding genes with those in other Ranunculaceae chloroplast DNAs showed that the chloroplast genome of A. austrokoreense is closely related to that of A. chiisanense and large sequence variations identified in rps16, matK, and rpl20 are specific to these two species.

Compounded direct pixel beamforming for medical ultrasound imaging.

In this paper, a new compounded direct pixel beamforming (CDPB) method is presented to remove blurring artifacts introduced by ultrasound scan conversion. In CDPB, receive focusing is directly performed on each display pixel in Cartesian coordinates using the raw RF data from adjacent transmit firings so that artifacts from the scan conversion can be removed. In addition, the energy variations resulting from the distance between the transmit scanline and display pixel are compensated by utilizing the gain factor obtained from the ultrasound beam pattern. The proposed CDPB method was evaluated using simulation and in vivo liver data acquired by a commercial ultrasound machine equipped with a research package. The experimental results showed that the proposed CDPB method improved the information entropy contrast (IEC) by 23.6% compared with the conventional scan conversion method and it reduced the blocking artifacts factor (BAF) by 16.4% over the direct pixel-based focusing method. These results indicate the proposed new direct pixel beamforming method could be used to enhance image quality in medical ultrasound imaging.