Copper-surface-mediated synthesis of sp2 carbon-conjugated covalent organic framework photocathodes for photoelectrochemical hydrogen evolution.

Sp2-carbon (sp2-c) covalent organic frameworks (COFs), featuring distinctive π-conjugated network structures, facilitate the migration of photo-generated carriers, rendering them exceptionally appealing for applications in photoelectrochemical water splitting. However, owing to the powdery nature of COFs, leaving anchor the sp2-c COFs powder tightly onto a conductive substrate challenging. Here, we propose a method for preparing photoactive substance-conductive substrate integrated photocathodes through copper surface-mediated knoevenagel polycondensation (Cu-SMKP), this approach results in a uniform and stable sp2-c COF film, directly grown on commercial copper foam (COFTh-Cu). The COFTh-Cu demonstrates a high H2-evolution photocurrent density of 56 µA cm-2 at 0.3 V versus RHE, sustaining stability for 12 hours. The as-prepared COFTh-Cu represents a 4.5-fold increase in current density compared to traditional spin-coating methods and outperforms most COF photocathodes without cocatalysts. This innovative copper surface-mediated approach for preparing photocathodes opens up a crucial pathway towards the realization of highly active COF photocathodes.

Highly dispersed ultrafine Ru nanoparticles on a honeycomb-like N-doped carbon matrix with modified rectifying contact for enhanced electrochemical hydrogen evolution.

The manipulation of rectifying contact between metal and semiconductor represents a powerful strategy to modify the electronic configuration of active sites for improved electrocatalytic performance. Herein, we present an NaCl template-assisted approach to rationally construct a Schottky electrocatalyst consisting of a honeycomb-like N-doped carbon matrix decorated with uniformly ultrasmall Ru nanoparticles with an average diameter of 2.5 nm (hereafter abbreviated as Ru NPs@HNC). It is found that the Fermi level difference between Ru and HNC can cause self-driven migration of electrons from Ru NPs to the HNC substrate, which leads to the generation of a built-in electric field and directional flow of electrons, thereby enhancing the intrinsic activity. In addition, the immobilization of ultrafine Ru NPs on the honeycomb-like carbon skeleton can effectively inhibit the undesired migration, agglomeration and detachment of the active sites, thus ensuring remarkable structural stability. As a result, the Ru NPs@HNC with optimal rectifying contact delivers superior electrochemical activity with a small overpotential of 28 mV at 10 mA cm-2 and outstanding long-term stability in an alkaline solution. The design philosophy of grain-size modulation and Schottky contact may widen up insight into the preparation of high-performance electrocatalysts in sustainable energy conversion systems.

Gravitational instability in a planet-forming disk.

The canonical theory for planet formation in circumstellar disks proposes that planets are grown from initially much smaller seeds1-5. The long-considered alternative theory proposes that giant protoplanets can be formed directly from collapsing fragments of vast spiral arms6-11 induced by gravitational instability12-14-if the disk is gravitationally unstable. For this to be possible, the disk must be massive compared with the central star: a disk-to-star mass ratio of 1:10 is widely held as the rough threshold for triggering gravitational instability, inciting substantial non-Keplerian dynamics and generating prominent spiral arms15-18. Although estimating disk masses has historically been challenging19-21, the motion of the gas can reveal the presence of gravitational instability through its effect on the disk-velocity structure22-24. Here we present kinematic evidence of gravitational instability in the disk around AB Aurigae, using deep observations of 13CO and C18O line emission with the Atacama Large Millimeter/submillimeter Array (ALMA). The observed kinematic signals strongly resemble predictions from simulations and analytic modelling. From quantitative comparisons, we infer a disk mass of up to a third of the stellar mass enclosed within 1″ to 5″ on the sky.

Deliberate Amorphization of Co-MOF for Constructing Crystalline-Amorphous Heterostructures Toward High-Performance Water Electrolysis.

The endowment of metal organic frameworks (MOF) with superior electrocatalytic performance without compromising their structural/compositional superiorities is of great significance for the development of renewable energy devices, yet remains a grand challenge. Herein, a deliberate partial amorphization strategy is developed to construct a heterostructured electrocatalyst consisting of crystalline Co-MOF and amorphous Co-S nanoflake arrays aligned on the carbon cloth (CC) substrate (abbreviated as Co-MOF/Co-S@CC hereafter) through a rapid sulfuration method. The simultaneous implement of crystalline-amorphous (c-a) heterostructure and nanoflake arrayed architecture on CC substrate renders the Co-MOF/Co-S@CC with abundant and tight active sites, accelerated charge transfer rate, regulated electronic structures, and reinforced structural stability. As such, the obtained Co-MOF/Co-S@CC electrode demonstrates outstanding electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of 64 and 217 mV at 10 mA cm-2, respectively. Moreover, a two-electrode electrolyzer assembled by Co-MOF/Co-S@CC electrodes exhibits the lower cell voltages and larger current densities than those of Pt/C and RuO2 counterparts, excellent reversibility and prominent long-term stability, representing a great prospect for feasible H2 production. This adopted concept of c-a heterostructure for electronic regulation may bring about insightful inspiration for designing high-performance electrocatalysts for sustainable energy systems.

Identifying Highly Active and Selective Cobalt X-Ides for Electrocatalytic Hydrogenation of Quinoline.

Earth-abundant Co X-ides are emerging as promising catalysts for the electrocatalytic hydrogenation of quinoline (ECHQ), yet challenging due to the limited fundamental understanding of ECHQ mechanism on Co X-ides. This work identifies the catalytic performance differences of Co X-ides in ECHQ and provides significant insights into the catalytic mechanism of ECHQ. Among selected Co X-ides, the Co3O4 presents the best ECHQ performance with a high conversion of 98.2% and 100% selectivity at ambient conditions. The Co3O4 sites present a higher proportion of 2-coordinated hydrogen-bonded water at the interface than other Co X-ides at a low negative potential, which enhances the kinetics of subsequent water dissociation to produce H*. An ideal 1,4/2,3-H* addition pathway on Co3O4 surface with a spontaneous desorption of 1,2,3,4-tetrahydroquinoline is demonstrated through operando tracing and theoretical calculations. In comparison, the Co9S8 sites display the lowest ECHQ performance due to the high thermodynamic barrier in the H* formation step, which suppresses subsequent hydrogenation; while the ECHQ on Co(OH)F and CoP sites undergo the 1,2,3,4- and 4,3/1,2-H* addition pathway respectively with the high desorption barriers and thus low conversion of quinoline. Moreover, the Co3O4 presents a wide substrate scope and allows excellent conversion of other quinoline derivatives and N-heterocyclic substrates.

Functional surfactant-directing ultrathin metallic nanoarchitectures as high-performance electrocatalysts.

Ultrathin nanosheets possess a distinctive structure characterized by an abundance of active sites fully accessible on their surface. Concurrently, their nanoscale thickness confers an extraordinarily high specific surface area and promising electronic properties. To date, numerous strategies have been devised for synthesizing precious metal nanosheets that exhibit excellent electrocatalytic performance. In this paper, recent progress in the controlled synthesis of two-dimensional, ultrathin nanosheets by a self-assembly mechanism using functional surfactants is reviewed. The aim is to highlight the key role of functional surfactants in the assembly and synthesis of two-dimensional ultrathin nanosheets, as well as to discuss in depth how to enhance their electrochemical properties, thereby expanding their potential applications in catalysis. We provide a detailed exploration of the mechanisms employed by several long-carbon chain surfactants commonly used in the synthesis of nanosheets. These surfactants exhibit robust electrostatic and hydrophobic effects, effectively confining the crystalline growth of metals along lamellar micelles. Moreover, we present an overview of the electrocatalytic performance demonstrated by the ultrathin nanosheets synthesized through this innovative pathway. Furthermore, it offers valuable insights that may pave the way for further exploration of more functional long-chain surfactants, leading to the synthesis of ultrathin nanosheets with significantly enhanced electrocatalytic performance.

Coordination Desymmetrization of Copper Single-Atom Catalyst for Efficient Nitrate Reduction.

Coordination engineering strategy for optimizing the catalytic performance of single-atom catalysts (SACs) has been rapidly developed over the last decade. However, previous reports on copper SACs for nitrate reduction reactions (NO3RR) have mostly focused on symmetric coordination configurations such as Cu-N4 and Cu-N3. In addition, the mechanism in terms of the regulation of coordination environment and catalytic properties of SACs has not been well demonstrated. Herein, we disrupted the local symmetric structure of copper atoms by introducing unsaturated heteroatomic coordination of Cu-O and Cu-N to achieve the coordination desymmetrization of Cu-N1O2 SACs. The Cu-N1O2 SACs exhibit an efficient nitrate-to-ammonia conversion with a high FE of ~96.5 % and a yield rate of 3120 µg NH3 h-1 cm-2 at -0.60 V vs RHE. As indicated by in situ Raman spectra, the catalysts facilitate the accumulation of NO3 - and the selective adsorption of *NO2, which were further confirmed by the theoretical study of surface dipole moment and orbital hybridization. Our work illustrated the correlation between the coordination desymmetrization and the catalytic performance of copper SACs for NO3RR.

Self-assembled high-entropy Prussian blue analogue nanosheets enabling efficient sodium storage.

High entropy material (HEM) has emerged as an appealing material platform for various applications, and specifically, the electrochemical performances of HEM could be further improved through self-assembled structure design. However, it remains a big challenge to construct such high-entropy self-assemblies primarily due to the compositional complexity. Herein, we propose a bottom-up directional freezing route to self-assemble high-entropy hydrosols into porous nanosheets. Taking Prussian blue analogue (PBA) as an example, the simultaneous coordination-substitution reactions yield stable high-entropy PBA hydrosols. During subsequent directional freezing process, the anisotropic growth of ice crystals could guide the two-dimensional confined assembly of colloidal nanoparticles, resulting in high-entropy PBA nanosheets (HE-PBA NSs). Thanks to the high-entropy and self-assembled structure design, the HE-PBA NSs manifests markedly enhanced sodium storage kinetics and performances in comparison with medium/low entropy nanosheets and high entropy nanoparticles.

Highly sensitive hydrolytic nanozyme-based sensors for colorimetric detection of aluminum ions.

Hydrolytic nanozyme-based visual colorimetry has emerged as a promising strategy for the detection of aluminum ions. However, most studies focus on simulating the structure of natural enzymes while neglecting to regulate the rate of hydrolysis-related steps, leading to low enzyme-like activity for hydrolytic nanozymes. Herein, we constructed a ruthenium dioxide (RuO2) in situ embedded cerium oxide (CeO2) nanozyme (RuO2/CeO2) with a Lewis acid-base pair (Ce-O-Ru-OH), which can simulate the catalytic behavior of phosphatase (PPase) and can be quantitatively quenched by Al3+ to achieve accurate and sensitive Al3+ colorimetric sensing detection. The incorporation of Ru into CeO2 nanorods accelerates the dissociation of H2O, followed by subsequent combination of hydroxide species to Lewis acidic Ce-O sites. This synergistic effect facilitates substrate activation and significantly enhances the hydrolysis activity of the nanozyme. The results show that the RuO2/CeO2 nanozyme exhibits a limit of detection as low as 0.5 ng/mL. We also demonstrate their efficacy in detecting Al3+ in various practical food samples. This study offers novel insights into the advancement of highly sensitive hydrolytic nanozyme engineering for sensing applications.

Toward Functionality and Deactivation of Metal-Single-Atom in Heterogeneous Photocatalysts.

Single-atom heterogeneous catalysts (SAHCs) provide an enticing platform for understanding catalyst structure-property-performance relationships. The 100% atom utilization and adjustable local coordination configurations make it easy to probe reaction mechanisms at the atomic level. However, the progressive deactivation of metal-single-atom (MSA) with high surface energy leads to frequent limitations on their commercial viability. This review focuses on the atomistic-sensitive reactivity and atomistic-progressive deactivation of MSA to provide a unifying framework for specific functionality and potential deactivation drivers of MSA, thereby bridging function, purpose-modification structure-performance insights with the atomistic-progressive deactivation for sustainable structure-property-performance accessibility. The dominant functionalization of atomically precise MSA acting on properties and reactivity encompassing precise photocatalytic reactions is first systematically explored. Afterward, a detailed analysis of various deactivation modes of MSA and strategies to enhance their durability is presented, providing valuable insights into the design of SAHCs with deactivation-resistant stability. Finally, the remaining challenges and future perspectives of SAHCs toward industrialization, anticipating shedding some light on the next stage of atom-economic chemical/energy transformations are presented.

Cyanogel-Induced Facile Synthesis of Palladium Hydride for Electrocatalytic Oxygen Reduction.

Palladium hydride (PdHx) is one of the well-known electrocatalytic materials, yet its synthesis is still a challenge through an energy-efficient and straightforward method. Herein, we propose a new and facile cyanogel-assisted synthesis strategy for the preparation of PdH0.649 at a mild environment with NaBH4 as the hydrogen source. Unlike traditional inorganic Pd precursors, the unique Pd-CN-Pd bridge in Pdx[Pd(CN)4]y ⋅ aH2O cyanogel offers more favourable spatial sites for insertion of H atoms. The characteristic three-dimensional backbone of cyanogel also acts as a support scaffold resulting in the interconnected network structure of PdH0.649. Due to the incorporation of H atoms and interconnected network structure, the PdH0.649 achieves a high half-wave potential of 0.932 V, a high onset potential of 1.062 V, and a low activation energy, as well as a long-term lifetime for oxygen reduction reaction. Theoretical calculation demonstrates a downshift of the d-band centre of Pd in PdH0.649 owing to the dominant Pd-H incorporation that weakens the binding energies of the *OH intermediate species. Zn-air batteries (ZAB) based on PdH0.649 exhibits high power density, competitive open circuit voltage, and good stability, exceeding that of commercial Pt black. This work not only opens up a new avenue for the development of high-efficiency Pt-free catalysts but also provides an original approach and insight into the synthesis of PdHx.

Perspective on High-Stability Single-Crystal Li-Rich Cathode Materials for Li-Ion Batteries.

Benefiting from anionic and cationic redox reactions, Li-rich materials have been regarded as next-generation cathodes to overcome the bottleneck of energy density. However, they always suffer from cracking of polycrystalline (PC) secondary particles and lattice oxygen release, resulting in severe structural deterioration and capacity decay upon cycling. Single-crystal (SC) design has been proven as an effective strategy to relieve these issues in traditional Li-rich cathodes with PC morphology. Herein, we first reviewed the main synthesis routes of SC Li-rich materials including solid-state reaction, molten salt-assisted, and hydrothermal/solvothermal methods, in which the differences in grain morphology, electrochemical behaviors, and other properties induced by various routes were analyzed and discussed. Furthermore, the distinct characteristics were compared between SC and PC cathodes from the aspects of irreversible capacity, structural stability, capacity/voltage degradation, and gas release. Besides, recent advances in layered SC Li-rich oxide cathodes were summarized in detail, where the unique structural designs and modification strategies could greatly promote their structural/electrochemical stability. At last, challenges and perspectives for the emerging SC Li-rich cathodes were proposed, which provided an exceptional opportunity to achieve high-energy-density and high-stability Li-ion/metal batteries.

Use of spectroscopic process analytical technology for rapid quality evaluation during preparation of CHO cell culture media.

Media preparation parameters contribute significantly to media quality, cell culture performance, productivity, and product quality. Establishing proper media preparation procedures is critical for ensuring a robust CHO cell culture process. Process analytical technology (PAT) enables unique ways to quantify assessments and improve media quality. Here, cell culture media were prepared under a wide range of temperatures (40-80°C) and pH (7.6-10.0). Media quality profiles were compared using three real-time PATs: Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, and excitation-emission matrix (EEM) spectroscopy. FTIR and Raman spectroscopies identified shifts in media quality under high preparation temperature (80°C) and at differing preparation pH which negatively impacted monoclonal antibody (mAb) production. In fed-batch processes for production of three different mAbs, viable cell density (VCD) and cell viability were mostly unaffected under all media preparation temperatures, while titer and cell specific productivity of mAb decreased when cultured in basal and feed media prepared at 80°C. High feed preparation pH alone was tolerated but cell growth and productivity profiles deviated from the control condition. Further, charge variants (main, acidic, basic species) and glycosylation (G0F, afucosylation, and high mannose) were examined. Statistically significant differences were observed for one or more of these quality attributes with any shifts in media preparation. In this study, we demonstrated strong associations between media preparation conditions and cell growth, productivity, and product quality. The rapid evaluation of media by PAT implementation enabled more comprehensive understanding of different parameters on media quality and consequential effects on CHO cell culture.

Single-embryo transcriptomic atlas of oxygen response reveals the critical role of HIF-1α in prompting embryonic zygotic genome activation.

Adaptive response to physiological oxygen levels (physO2; 5% O2) enables embryonic survival in a low-oxygen developmental environment. However, the mechanism underlying the role of physO2 in supporting preimplantation development, remains elusive. Here, we systematically studied oxygen responses of hallmark events in preimplantation development. Focusing on impeded transcriptional upregulation under atmospheric oxygen levels (atmosO2; 20% O2) during the 2-cell stage, we functionally identified a novel role of HIF-1α in promoting major zygotic genome activation by serving as an oxygen-sensitive transcription factor. Moreover, during blastocyst formation, atmosO2 impeded H3K4me3 and H3K27me3 deposition by deregulating histone-lysine methyltransferases, thus impairing X-chromosome inactivation in blastocysts. In addition, we found atmosO2 impedes metabolic shift to glycolysis before blastocyst formation, thus resulting a low-level histone lactylation deposition. Notably, we also reported an increased sex-dimorphic oxygen response of embryos upon preimplantation development. Together, focusing on genetic and epigenetic events that are essential for embryonic survival and development, the present study advances current knowledge of embryonic adaptive responses to physO2, and provides novel insight into mechanism underlying irreversibly impaired developmental potential due to a short-term atmosO2 exposure.

Fed-batch performance profiles for mAb production using different intensified N - 1 seed strategies are CHO cell-line dependent.

Recent optimizations of cell culture processes have focused on the final seed scale-up step (N - 1 stage) used to inoculate the production bioreactor (N-stage bioreactor) to enable higher inoculation cell densities (2-20 × 106 cells/mL), which could shorten the production culture duration and/or increase the volumetric productivity. N - 1 seed process intensification can be achieved by either non-perfusion (enriched-batch or fed-batch) or perfusion culture to reach those higher final N - 1 viable cell densities (VCD). In this study, we evaluated how different N - 1 intensification strategies, specifically enriched-batch (EB) N - 1 versus perfusion N - 1, affect cell growth profiles and monoclonal antibody (mAb) productivity in the final N-stage production bioreactor operated in fed-batch mode. Three representative Chinese Hamster Ovary (CHO) cell lines producing different mAbs were cultured using either EB or perfusion N - 1 seeds and found that the N-stage cell growth and mAb productivities were comparable between EB N - 1 and perfusion N - 1 conditions for two of the cell lines but were very different for the third. In addition, within the two similar cell growth cell lines, differences in cell-specific productivity were observed. This suggests that the impact of the N - 1 intensification process on production was cell-line dependent. This study revealed that the N - 1 intensification strategy and the state of seeds from the different N - 1 conditions may affect the outcome of the N production stage, and thus, the choice of N - 1 intensification strategy could be a new target for future upstream optimization of mAb production.

Low-loaded Ru on hollow SnO2 for enhanced electrocatalytic hydrogen evolution.

In response to the challenges of intermediate poisoning and the high cost of noble metal catalysts in the hydrogen evolution reaction (HER), we develop a Ru-doped SnO2 catalyst. This Ru-SnO2 catalyst has the characteristics of low Ru loading and a hollow structure, which endow it with good electrocatalytic activity and stability for the HER.

Role of amorphous engineering and cerium doping in NiFe oxyhydroxide for electrocatalytic water oxidation.

Amorphous engineering and atomistic doping provide an effective way to improve the catalytic activity in the oxygen evolution reaction (OER) of transition metal layered double hydroxides. Herein, Cerium (Ce) was introduced into NiFe-based oxyhydroxide using a modified aqueous sol-gel procedure. Ce as an electron acceptor promoted the coupling oxidation of Ni2+/3+ in NiFe oxyhydroxide, and the activated oxyhydroxide showed excellent catalytic activity in OER. The amorphous NiFeCe oxyhydroxide electrocatalyst demonstrated great modified OER catalytic activity under alkaline conditions and excellent cyclic stability, with an overpotential of only 284 mV at 50 mA cm-2, which was significantly better than amorphous NiFe oxyhydroxide and crystalline NiFeCe oxyhydroxide. Theoretical investigations further indicated that the overpotential of the rate-determining step (*OOH deprotonation) decreased from 0.66 to 0.41 V after Ce doping and strong electron interaction, effectively reducing the dependence of proton activity in the solution of OER, and optimizing the adsorption/desorption process of related oxygen-containing species in the reaction. This work also provides a good reference for optimizing OER activity by using rare-earth-metal induced electronic regulation strategies.

Effect of intubation in lateral position on placement of a double-lumen tube in patients undergoing unilateral video-assisted thoracic surgery: a randomied clinical trial.

Background: Approximately one-third of patients who undergo double-lumen tube (DLT) intubation in the conventional supine position experience DLT malposition. No randomized study investigates the effect of DLT intubation in the lateral position. We therefore aimed to evaluate the effect of intubation in lateral position on placement of a DLT compared to supine intubation, and to test primary hypothesis that lateral DLT intubation could reduce the incidence of DLT malposition. Methods: We randomly allocated 108 patients undergoing video-assisted thoracic surgery to receive DLT intubation in the comfortable and surgically required lateral position (lateral group) or in the supine position (supine group) from October to December 2022. The primary outcome was the incidence of DLT malposition defined as movement >1.0 cm to correct the DLT position. The secondary outcomes included intubation time, the frequency and duration of fibreoptic bronchoscopy, the need for re-intubation, intra-operative vital signs, and post-operative recovery. This trial is registered with the Chinese Clinical Trial Registry (ChiCTR2200060794). Findings: The incidence of DLT malposition was significantly lower in the lateral group (1/53 [2%]) than that in the supine group (16/53 [30%]; RR [95% confidence interval] of 0.06 [0.01-0.46]; P < 0.001). Lateral DLT intubation decreased the intubation time, the frequency and duration of fibreoptic bronchoscopy. The incidence of hypotension, post-operative sore throat, and upper-arm discomfort was lower in the lateral group. Other secondary outcomes were similar between groups. Interpretation: Lateral DLT intubation reduced the incidence of DLT malposition for patients undergoing video-assisted thoracic surgery. These results support that lateral DLT intubation offers more benefits and may be a superior option compared to conventional supine intubation. Funding: National Natural Science Foundation of China and of Zhejiang Province.

Recent advances in upstream process development for production of recombinant adeno-associated virus.

Recombinant adeno-associated virus (rAAV) is rapidly emerging as the preferred delivery vehicle for gene therapies, with promising advantages in safety and efficacy. Key challenges in systemic in-vivo rAAV gene therapy applications are the gap in production capabilities versus potential market demand and complex production process. This review summarizes current available information on rAAV upstream manufacturing processes and proposed optimizations for production. The advancements in rAAV production media were reviewed with proposals to speed up the cell culture process development. Furthermore, major methods for genetic element delivery to host cells were summarized with their advantages, limitations, and future directions for optimization. In addition, culture vessel selection criteria were listed based on production cell system, scale, and development stage. Process control at the production step was also outlined with an in-depth understanding of production kinetics and quality control.

Single-Atom Heterogeneous Catalysts: Human- and AI-Driven Platform for Augmented Designs, Analytics and Reality-Enabled Manufacturing.

Heterogeneous catalysts with targeted functionality can be designed with atomic precision, but it is challenging to retain the structure and performance upon the scaled-up manufacturing. Particularly challenging is to ensure the "atomic economy", where every catalytic site is most gainfully utilized. Given the emerging synergistic integration of human- and artificial intelligence (AI)-driven augmented designs (AD), augmented analytics (AA), and augmented reality manufacturing (AM) platforms, this minireview focuses on single-atom heterogeneous catalysts (SAHCs) and examines the current status, challenges, and future perspectives of translating atomic-level structural precision and data-driven discovery to next-generation industrial manufacturing. We critically examine the atomistic insights into structure-driven SAHCs functionality and discuss the opportunities and challenges on the way towards the synergistic human-AI collaborative data-driven platform capable of monitoring, analyzing, manufacturing, and retaining the atomic-scale structure and functions. Enhanced by the atomic-level AD, AA, and AM, evolving from the current high-throughput capabilities and digital materials manufacturing acceleration, this synergistic human-AI platform is promising to enable atom-efficient and atomically precise heterogeneous catalyst production.