Facet-switching of rate-determining step on copper in CO2-to-ethylene electroreduction.

Reduction of carbon dioxide (CO2) by renewable electricity to produce multicarbon chemicals, such as ethylene (C2H4), continues to be a challenge because of insufficient Faradaic efficiency, low production rates, and complex mechanistic pathways. Here, we report that the rate-determining steps (RDS) on common copper (Cu) surfaces diverge in CO2 electroreduction, leading to distinct catalytic performances. Through a combination of experimental and computational studies, we reveal that C─C bond-making is the RDS on Cu(100), whereas the protonation of *CO with adsorbed water becomes rate-limiting on Cu(111) with a higher energy barrier. On an oxide-derived Cu(100)-dominant Cu catalyst, we reach a high C2H4 Faradaic efficiency of 72%, partial current density of 359 mA cm-2, and long-term stability exceeding 100 h at 500 mA cm-2, greatly outperforming its Cu(111)-rich counterpart. We further demonstrate constant C2H4 selectivity of >60% over 70 h in a membrane electrode assembly electrolyzer with a full-cell energy efficiency of 23.4%.

Simulation and mechanism for the Ultrasound-Assisted Oiling-Out Process: A case study using Fructose-1,6-diphosphate.

Liquid-liquid separation, commonly referred to as oiling-out, frequently can occurs during crystallization, especially the anti-solvent crystallization process of phosphoryl compounds, and poses potential hurdle for high-quality product. Efficiently regulating oiling-out during crystallization remains a significant challenge. Among various techniques, ultrasound emerges as a green and effective approach to enhance the crystallization process. However, there is a dearth of in-depth research exploring the microscopic mechanisms of this process. Therefore, our research focused on the fructose-1,6-diphosphate (FDP), a typical phosphoryl compound, to gain a deeper understanding of how ultrasound influences the oiling-out process. The focused beam reflectance measurement (FBRM) technology was used to investigate the oiling-out phenomenon of FDPNa3 across various solvent ratios. In addition, the influence of ultrasound on the induction time was studied and the nucleation energy barrier was calculated. Finally, to further unravel the microscopic mechanisms, we utilized molecular simulation techniques to analyze the impact of ultrasound power on the dissolution-precipitation process. Our observations revealed a consistent oiling-out process that attainted a stable state regardless of the solvent employed. Notably, the results of the oiling-out induction time experiments indicated that ultrasound significantly reduced helped lower the nucleation energy barrier of FDP3- ions, thereby dismantling FDP3-clusters in solution. Thus, in turn, shortened the reduced induction time and promoted crystallization. Furthermore, ultrasound reduced the interactions between FDP3-ions and water molecules as well as FDP3- ions themselves. As simulated field intensity increased, these interaction forces gradually diminished, the thickness of the hydration layer surrounding the FDP3- clusters facilitating the disruption of clusters, ultimately enhancing the crystallization process.

Meta-Analysis of Efficacy of Platelet-Rich Plasma Combined with Minoxidil for Androgenetic Alopecia.

BACKGROUND: Androgenetic alopecia (AGA) is a prevalent type of hair loss that impacts individuals of both genders. Platelet-rich plasma (PRP) and minoxidil have been employed as therapeutic interventions for AGA, yet the efficacy of their concurrent use remains ambiguous. OBJECTIVE: To perform a comprehensive review and meta-analysis aimed at evaluating the effectiveness of platelet-rich plasma (PRP) in combination with minoxidil for the treatment of androgenetic alopecia (AGA). METHODS: We conducted a comprehensive search of the databases PubMed, Embase, Web of Science, and Cochrane Library, encompassing their complete records up until December 2023. Eligible studies were randomized controlled trials that compared the combination of PRP and minoxidil with minoxidil or PRP alone in patients with AGA. The primary outcome measure was the change in hair growth as assessed by the hair density or hair thickness. Secondary outcome measures included patient satisfaction, and global photographic assessment. RESULTS: A total of 6 studies involving 343 participants were included in this meta-analysis. The results showed that PRP combined with minoxidil significantly improved hair growth compared to minoxidil or PRP alone. The pooled analysis demonstrated a significant increase in hair density (weighted mean difference [WMD] = 9.14; 95% confidence interval [CI]: 6.57-11.70) and hair diameter (WMD = 4.72; 95% CI 3.21-6.23) in the PRP combined with minoxidil group. Moreover, patients receiving PRP combined with minoxidil reported higher satisfaction rates compared to those using minoxidil or PRP alone. CONCLUSIONS: This meta-analysis suggests that PRP combined with minoxidil is an effective treatment for AGA, providing significant improvement in hair growth and patient satisfaction. LEVEL OF EVIDENCE III: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .

Unraveling Stoichiometry Effect in Nickel-Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes.

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni : W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

Long-Chain Bio-Based Nylon 514 Salt: Crystal Structure, Phase Transformation, and Polymerization.

Nylon 514 is one of the new long-chain bio-based nylon materials; its raw material, 1,5-pentanediamine (PDA), is prepared by biological techniques, using biomass as the raw material. The high-performance monomer of nylon 514, 1,5-pentanediamine-tetradecanedioate (PDA-TDA) salt, was obtained through efficient crystallization methods. Here, two crystal forms of PDA-TDA, anhydrous and dihydrate, were identified and studied in this paper. From the characterization data, their crystal structures and thermal behaviors were investigated. Lattice energy was calculated to gain further insight into the relationship between thermal stability and crystal structures. The contribution of hydrogen bonds and other intermolecular interactions to the crystal structure stability have been quantified according to detailed Hirshfeld and IRI analyses. Additionally, the transformation mechanism of the anhydrate and dihydrate was established through a series of well-designed stability experiments, in which the temperature and water activity play a significant role in the structural stability of crystalline forms. Eventually, we obtained nylon 514 products with good thermal stability and low absorption using stable dihydrate powders as monomers. The properties of nylon 514 products prepared by different polymerization methods were also compared.

Long-term in vivo chimeric cells tracking in non-human primate.

Non-human primates (NHPs) are increasingly used in preclinical trials to test the safety and efficacy of biotechnology therapies. Nonetheless, given the ethical issues and costs associated with this model, it would be highly advantageous to use NHP cellular models in clinical studies. However, developing and maintaining the naïve state of primate pluripotent stem cells (PSCs) remains difficult as does in vivo detection of PSCs, thus limiting biotechnology application in the cynomolgus monkey. Here, we report a chemically defined, xeno-free culture system for culturing and deriving monkey PSCs in vitro. The cells display global gene expression and genome-wide hypomethylation patterns distinct from monkey-primed cells. We also found expression of signaling pathways components that may increase the potential for chimera formation. Crucially for biomedical applications, we were also able to integrate bioluminescent reporter genes into monkey PSCs and track them in chimeric embryos in vivo and in vitro. The engineered cells retained embryonic and extra-embryonic developmental potential. Meanwhile, we generated a chimeric monkey carrying bioluminescent cells, which were able to track chimeric cells for more than 2 years in living animals. Our study could have broad utility in primate stem cell engineering and in utilizing chimeric monkey models for clinical studies.

Gerhardtite as a Precursor to an Efficient CO-to-Acetate Electroreduction Catalyst.

Carbon-carbon coupling electrochemistry on a conventional copper (Cu) catalyst still undergoes low selectivity among many different multicarbon (C2+) chemicals, posing a grand challenge to achieve a single C2+ product. Here, we demonstrate a laser irradiation synthesis of a gerhardtite mineral, Cu2(OH)3NO3, as a catalyst precursor to make a Cu catalyst with abundant stacking faults under reducing conditions. Such structural perturbation modulates electronic microenvironments of Cu, leading to improved d-electron back-donation to the antibonding orbital of *CO intermediates and thus strengthening *CO adsorption. With increased *CO coverage on the defect-rich Cu, we report an acetate selectivity of 56 ± 2% (compared to 31 ± 1% for conventional Cu) and a partial current density of 222 ± 7 mA per square centimeter in CO electroreduction. When run at 400 mA per square centimeter for 40 h in a flow reactor, this catalyst produces 68.3 mmol of acetate throughout. This work highlights the value of a Cu-containing mineral phase in accessing suitable structures for improved selectivity to a single desired C2+ product.

Efficient NH3-Tolerant Nickel-Based Hydrogen Oxidation Catalyst for Anion Exchange Membrane Fuel Cells.

Converting hydrogen chemical energy into electrical energy by fuel cells offers high efficiencies and environmental advantages, but ultrapure hydrogen (over 99.97%) is required; otherwise, the electrode catalysts, typically platinum on carbon (Pt/C), will be poisoned by impurity gases such as ammonia (NH3). Here we demonstrate remarkable NH3 resistivity over a nickel-molybdenum alloy (MoNi4) modulated by chromium (Cr) dopants. The resultant Cr-MoNi4 exhibits high activity toward alkaline hydrogen oxidation and can undergo 10,000 cycles without apparent activity decay in the presence of 2 ppm of NH3. Furthermore, a fuel cell assembled with this catalyst retains 95% of the initial peak power density even when NH3 (10 ppm)/H2 was fed, whereas the power output reduces to 61% of the initial value for the Pt/C catalyst. Experimental and theoretical studies reveal that the Cr modifier not only creates electron-rich states that restrain lone-pair electron donation but also downshifts the d-band center to suppress d-electron back-donation, synergistically weakening NH3 adsorption.

Solubility, Crystallization, and Characterization of Cytidine Sulfate.

Cytidine is an important kind of nucleoside that can be applied to drug development and food industry. Cytidine sulfate is one of its popular forms, which is promising as a medicinal intermediate, especially in antiviral and antitumor drugs. Product refining is the key point of industrial development, and crystallization is a significant way of refining. In this work, the solubility of cytidine sulfate in pure water from 278.15 to 328.15 K and in water-ethanol binary solvents at 298.15 K was measured by the UV spectroscopic method. The solubility data were correlated with temperature and solvent composition using the modified Apelblat, van't Hoff, and CNIBS/R-K equations. On this basis, we investigated and compared three crystallization processes, and the coupling method was developed to prepare crystals with a large particle size, concentrated distribution, and high yield and packing density. In addition, the structure and stability of the products were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and dynamic vapor sorption analysis. It was found that cytidine sulfate has only one crystal form in our research process, and the product of coupling crystallization is stable and favorable for industrial development.

Efficient acidic hydrogen evolution in proton exchange membrane electrolyzers over a sulfur-doped marcasite-type electrocatalyst.

Large-scale deployment of proton exchange membrane (PEM) water electrolyzers has to overcome a cost barrier resulting from the exclusive adoption of platinum group metal (PGM) catalysts. Ideally, carbon-supported platinum used at cathode should be replaced with PGM-free catalysts, but they often undergo insufficient activity and stability subjecting to corrosive acidic conditions. Inspired by marcasite existed under acidic environments in nature, we report a sulfur doping-driven structural transformation from pyrite-type cobalt diselenide to pure marcasite counterpart. The resultant catalyst drives hydrogen evolution reaction with low overpotential of 67 millivolts at 10 milliamperes per square centimeter and exhibits no degradation after 1000 hours of testing in acid. Moreover, a PEM electrolyzer with this catalyst as cathode runs stably over 410 hours at 1 ampere per square centimeter and 60°C. The marked properties arise from sulfur doping that not only triggers formation of acid-resistant marcasite structure but also tailors electronic states (e.g., work function) for improved hydrogen diffusion and electrocatalysis.

Spatiotemporal proteomic atlas of multiple brain regions across early fetal to neonatal stages in cynomolgus monkey.

Fetal stages are critical periods for brain development. However, the protein molecular signature and dynamics of the human brain remain unclear due to sampling difficulty and ethical limitations. Non-human primates present similar developmental and neuropathological features to humans. This study constructed a spatiotemporal proteomic atlas of cynomolgus macaque brain development from early fetal to neonatal stages. Here we showed that (1) the variability across stages was greater than that among brain regions, and comparisons of cerebellum vs. cerebrum and cortical vs. subcortical regions revealed region-specific dynamics across early fetal to neonatal stages; (2) fluctuations in abundance of proteins associated with neural disease suggest the risk of nervous disorder at early fetal stages; (3) cross-species analysis (human, monkey, and mouse) and comparison between proteomic and transcriptomic data reveal the proteomic specificity and genes with mRNA/protein discrepancy. This study provides insight into fetal brain development in primates.

Enrichment of reactants and intermediates for electrocatalytic CO2 reduction.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) presents a sustainable route to convert renewable electricity to value-added fuels and feedstocks in the form of chemical energy. However, the selectivity and rate of conversion of CO2 to desirable carbon-based products, especially multicarbon products, remain below the requirement for its implementation at the commercial scale, which primarily originates from inadequate reactants and intermediates near catalytic surfaces during the CO2RR. The enrichment of reactants and intermediates provides one of the coping guidelines to improve CO2RR performance by accelerating the reaction rate and improving product selectivity. Herein, we discuss strategies to achieve the enrichment of reactants and intermediates through catalyst design, local microenvironment modulation, electrolyte regulation, and electrolyzer optimization. The structure and properties of CO2 are first presented, showing the necessity and feasibility of enriching reactants and intermediates. Next, the influence of the enrichment effect on CO2 electrolysis, i.e., accelerating the reaction rate and improving product selectivity, are comprehensively discussed. Then, catalyst design from micrometer scale to atom scale, including wettability and morphology regulation, surface modification, and tandem structure construction, as well as surface atom engineering, is highlighted to implement the enrichment of reactants and intermediates. Catalyst restructuring during the CO2RR process and its impact on the enrichment of intermediates and reactants are also discussed. Subsequently, enriching CO2 reactants and intermediates by modulating the local microenvironment to achieve high carbon utilization for the CO2RR to produce multicarbon products is reviewed. After that, insights into enriching reactants and intermediates through electrolyte regulation are provided by investigating various electrolytes, including aqueous solutions, organic solvents, and ionic liquids. Additionally, the key role of electrolyzer optimization in promoting the enrichment effect is considered. We end the review by outlining the remaining technological challenges and providing feasible suggestions aimed at directing the future employment of enrichment strategies to propel the practical implementation of CO2 electrolysis technology.

Biofilm-Based Biocatalysis for Galactooligosaccharides Production by the Surface Display of ß-Galactosidase in Pichia pastoris.

Galactooligosaccharides (GOS) are one of the most important functional oligosaccharide prebiotics. The surface display of enzymes was considered one of the most excellent strategies to obtain these products. However, a rough industrial environment would affect the biocatalytic process. The catalytic process could be efficiently improved using biofilm-based fermentation with high resistance and activity. Therefore, the combination of the surface display of ß-galactosidase and biofilm formation in Pichia pastoris was constructed. The results showed that the catalytic conversion rate of GOS was up to 50.3% with the maximum enzyme activity of 5125 U/g by screening the anchorin, and the number of the continuous catalysis batches was up to 23 times. Thus, surface display based on biofilm-immobilized fermentation integrated catalysis and growth was a co-culture system, such that a dynamic equilibrium in the consolidated integrative process was achieved. This study provides the basis for developing biofilm-based surface display methods in P. pastoris during biochemical production processes.

Highly Enhanced Chloride Adsorption Mediates Efficient Neutral CO2 Electroreduction over a Dual-Phase Copper Catalyst.

Electrocatalytic carbon dioxide reduction (CO2R) in neutral electrolytes can mitigate the energy and carbon losses caused by carbonate formation but often experiences unsatisfied multicarbon selectivity and reaction rates because of the kinetic limitation to the critical carbon monoxide (CO)-CO coupling step. Here, we describe that a dual-phase copper-based catalyst with abundant Cu(I) sites at the amorphous-nanocrystalline interfaces, which is electrochemically robust in reducing environments, can enhance chloride-specific adsorption and consequently mediate local *CO coverage for improved CO-CO coupling kinetics. Using this catalyst design strategy, we demonstrate efficient multicarbon production from CO2R in a neutral potassium chloride electrolyte (pH ∼6.6) with a high Faradaic efficiency of 81% and a partial current density of 322 milliamperes per square centimeter. This catalyst is stable after 45 h of operation at current densities relevant to commercial CO2 electrolysis (300 mA per square centimeter).

Interfacial Engineering of Ni/V2 O3 Heterostructure Catalyst for Boosting Hydrogen Oxidation Reaction in Alkaline Electrolytes.

Alkaline fuel cells can permit the adoption of platinum group metal-free (PGM-free) catalysts and cheap bipolar plates, thus further lowering the cost. With the exploration of PGM-free hydrogen oxidation reaction (HOR) catalysts, nickel-based compounds have been considered as the most promising HOR catalysts in alkali. Here we report an interfacial engineering through the formation of nickel-vanadium oxide (Ni/V2 O3 ) heterostructures to activate Ni for efficient HOR catalysis in alkali. The strong electron transfer from Ni to V2 O3 could modulate the electronic structure of Ni sites. The optimal Ni/V2 O3 catalyst exhibits a high intrinsic activity of 0.038 mA cm-2 and outstanding stability. Experimental and theoretical studies reveal that Ni/V2 O3 interface as the active sites can enable to optimize the hydrogen and hydroxyl bindings, as well as protect metallic Ni from extensive oxidation, thus achieving the notable activity and durability.

The effect of polymorphism on polymer properties: crystal structure, stability and polymerization of the short-chain bio-based nylon 52 monomer 1,5-pentanediamine oxalate.

The compound 1,5-pentanediamine (PDA) is prepared by biological methods using biomass as raw material. The salt of 1,5-pentanediamine oxalate (PDA-OXA) was used directly as the monomer for the preparation of a new bio-based nylon 52 material. High-performance polymer materials require initial high-quality monomers, and crystallization is an essential approach to preparing such a monomer. In this work, three crystal forms of PDA-OXA, the anhydrate, dihydrate and trihydrate, were found and the single crystals of two hydrates were obtained. Their crystal structures were determined using single-crystal and powder X-ray diffraction. The thermal behaviors were characterized by thermodynamic analysis, and the lattice energy was calculated to further explore the relationship between the thermal stability and crystal structure. Detailed computational calculations, Hirshfeld analyses and lattice energy calculations were performed to quantify both the contribution of intra- and intermolecular interactions to the supramolecular assembly, as well as the influence on the stability of the structure. The structure-property relationship between the PDA-OXA crystal forms was established. Moreover, the phase transformation mechanism between the crystalline forms of PDA-OXA has been established, and the control strategy of specific crystal forms was developed from the water activity-temperature phase diagram and relevant thermodynamic data. Finally, the influence of the polymorphism of the monomer and the polymerization methods on the properties of the polymer was investigated. The nylon 52 product obtained showed good appearance, high hardness and thermal stability, the polymer made using the anhydrate as the monomer has better thermodynamic properties than that prepared from the dihydrate, indicating practical industrial application prospects.

SpringWorm: A Soft Crawling Robot with a Large-Range Omnidirectional Deformable Rectangular Spring for Control Rod Drive Mechanism Inspection.

In this article, a cable-driven elastic backbone worm-like robot (named "SpringWorm") of decimeter-level size is designed, which has high adaptability in crack inspection of the weld between reactor pressure vessel (RPV) and control rod drive mechanisms. The robot consists of a body that adopts a rectangular helix spring backbone driven by four cables and the flexible claws embedded with distributed electromagnets. Combining the omnidirectional deformation of the backbone and the passive deformation adsorption of the claws, the robot can achieve a variety of gaits. Based on the approaches of geometric analysis and transformation matrices of the coordinate frame, a kinematic model of the cable-driven backbone has been established. Moreover, a mechanical model considering the friction between the cable and the backbone has also been established. The top position and the bending angle of the backbone obtained by the theory, simulation, and experiment are in good agreement. In addition, the errors of the driving force between simulation and experimental results are also small. SpringWorm is 670 g, measures 206 × 65 × 75 mm, has a maximum speed of 8.9 mm/s, and has a maximum payload of 1 kg. The robot can climb over 2-cm-tall steps and 4-cm-deep ditches, and climb and turn on the vertical wall, on the pipe with a radius of 31 cm, and on the spherical surface of RPV.

Design and optimization of the continuous separation process for lignin and alkali by 'Extended Separation Volume' method.

This work is to design and optimize the 4column-simulated moving bed unit to separate and recovery alkali and lignin from black liquor. Since both alkali lignin and NaOH are the main products, we proposed the 'extended separation volume' methodology to construct a four-dimensional separation region (QI×QII×QIII×QIV) to design the operating conditions. Special attention was paid to investigate the influence of flow-rates in each zone on the performance parameters of these two products. The results show besides QII and QIII, QI and QIV can affect the concentrations and productivities significantly and have to be taken into account. Afterwards, the Response Surface Methodology, conducted by Design-Expert® was chosen to deal with the multi-objective optimization problem. The unique optimal operating conditions were finally obtained with the concentration of 74.7% and 48.1% of feed solution, and the productivity of 3.9 and 0.7 g/(L·h)-1 for alkali lignin and NaOH. Considering the actual operation, the productivity of 2.5 and 0.446 g/(L·h)-1 were obtained by experiment of internal actual operation point.

Speciation, bioaccessibility and human health risk assessment of chromium in solid wastes from an ultra-low emission coal-fired power plant, China.

Chromium (Cr) in solid wastes from ultra-low emission (ULE) coal-fired power plants (CFPPs) could engender adverse effects on environment and human health. Hence, solid waste samples containing bottom ash, fly ash, gypsum and sludge were collected from a typical ULE CFPP in China to study the distribution, speciation, bioaccessibility and human health risk of Cr. The results showed that Cr was depleted in gypsum, whereas significantly enriched in bottom ash, fly ash and sludge comparing with feed coal. The ratios of Cr(VI) to total Cr in solid wastes were relatively low, but the increase of flow fractions in Cr chemical binding forms implied the deterioration of environmental stability. Based on the in vitro simulated digestion methods of solubility bioavailability research consortium (SBRC) and physiologically based extraction test (PBET), the bioaccessibility of Cr in the gastric and intestinal phases reached the highest values in either gypsum or sludge. After incorporating bioaccessibility in human health risk assessment, the carcinogenic risk (CR) within acceptable limits of Cr in solid wastes to adults and children was concluded, with the non-carcinogenic hazard quotient (HQ) was all within the safety threshold. The Monte Carlo model was applied to evaluate the uncertainty analysis of human health risk assessment at 5% and 95% confidence interval, and the fitting results were consistent with the calculation results of the carcinogenic and non-carcinogenic risk for adults and children. This study is expected to provide insights for the integration of bioaccessibility into the health risk assessment of Cr in solid wastes from ULE CFPPs, thus is conducive to the disposal of solid wastes and human health protection.

Polymorph control by designed ultrasound application strategy: The role of molecular self-assembly.

Molecular self-assembly plays a vital role in the nucleation process and sometimes determines the nucleation outcomes. In this study, ultrasound technology was applied to control polymorph nucleation. For the first time, different ultrasonic application methods based on the nucleation mechanisms have been proposed. For PZA-water and DHB-toluene systems that the molecular self-assembly in solution resembles the synthon in crystal structure, ultrasound pretreatment strategy was conducted to break the original molecular interactions to alter the nucleated form. When the solute molecular self-associates can't give sufficient information to predict the nucleated polymorph like INA-ethanol system, the method of introducing continuous ultrasonic irradiation in the nucleation stage was applied. The induction of ultrasound during nucleation process can break the original interactions firstly by shear forces and accelerate the occurrence of nucleation to avoid the reorientation and rearrangement of solute molecules. These strategies were proved to be effective in polymorph control and have a degree of applicability.