Producing valuable chemicals like ethylene via catalytic carbon monoxide conversion is an important nonpetroleum route. Here we demonstrate an electrochemical route for highly efficient synthesis of multicarbon (C2+) chemicals from CO. We achieve a C2+ partial current density as high as 4.35 ± 0.07 A cm-2 at a low cell voltage of 2.78 ± 0.01 V over a grain boundary-rich Cu nanoparticle catalyst in an alkaline membrane electrode assembly (MEA) electrolyzer, with a C2+ Faradaic efficiency of 87 ± 1% and a CO conversion of 85 ± 3%. Operando Raman spectroscopy and density functional theory calculations reveal that the grain boundaries of Cu nanoparticles facilitate CO adsorption and C - C coupling, thus rationalizing a qualitative trend between C2+ production and grain boundary density. A scale-up demonstration using an electrolyzer stack with five 100 cm2 MEAs achieves high C2+ and ethylene formation rates of 118.9 mmol min-1 and 1.2 L min-1, respectively, at a total current of 400 A (4 A cm-2) with a C2+ Faradaic efficiency of 64%.
The Lrp/AsnC family of transcriptional regulators is commonly found in prokaryotes and is associated with the regulation of amino acid metabolism. However, it remains unclear how the L-cysteine-responsive Lrp/AsnC family regulator perceives and responds to L-cysteine. Here, we try to elucidate the molecular mechanism of the L-cysteine-responsive transcriptional regulator. Through 5'RACE and EMSA, we discovered a 15 bp incompletely complementary pair palindromic sequence essential for DecR binding, which differed slightly from the binding sequence of other Lrp/AsnC transcription regulators. Using alanine scanning, we identified the L-cysteine binding site on DecR and found that different Lrp/AsnC regulators adjust their binding pocket's side-chain residues to accommodate their specific effector. MD simulations were then conducted to explore how ligand binding influences the allosteric behavior of the protein. PCA and in silico docking revealed that ligand binding induced perturbations in the linker region, triggering conformational alterations and leading to the relocalization of the DNA-binding domains, enabling the embedding of the DNA-binding region of DecR into the DNA molecule, thereby enhancing DNA-binding affinity. Our findings can broaden the understanding of the recognition and regulatory mechanisms of the Lrp/AsnC-type transcription factors, providing a theoretical basis for further investigating the molecular mechanisms of other transcription factors.
L-cysteine is an important sulfur-containing amino acid being difficult to produce by microbial fermentation. Due to the lack of high-throughput screening methods, existing genetically engineered bacteria have been developed by simply optimizing the expression of L-cysteine-related genes one by one. To overcome this limitation, in this study, a biosensor-based approach for multilevel biosynthetic pathway optimization of L-cysteine from the DecR regulator variant of Escherichia coli was applied. Through protein engineering, we obtained the DecRN29Y/C81E/M90Q/M99E variant-based biosensor with improved specificity and an 8.71-fold increase in dynamic range. Using the developed biosensor, we performed high-throughput screening of the constructed promoter and RBS combination library, and successfully obtained the optimized strain, which resulted in a 6.29-fold increase in L-cysteine production. Molecular dynamics (MD) simulations and electrophoretic mobility shift analysis (EMSA) showed that the N29Y/C81E/M90Q/M99E variant had enhanced induction activity. This enhancement may be due to the increased binding of the variant to DNA in the presence of L-cysteine, which enhances transcriptional activation. Overall, our biosensor-based strategy provides a promising approach for optimizing biosynthetic pathways at multiple levels. The successful implementation of this strategy demonstrates its potential for screening improved recombinant strains.
Electrocatalytic acetylene semi-hydrogenation (EASH) offers a promising and environmentally friendly pathway for the production of C2H4, a widely used petrochemical feedstock. While the economic feasibility of this route has been demonstrated in three-electrode systems, its viability in practical device remains unverified. In this study, we designed a highly efficient electrocatalyst based on a PdCu alloy system utilizing the hydrogen spillover mechanism. The catalyst achieved an operational current density of 600 mA cm-2 in a zero-gap membrane electrode assembly (MEA) reactor, with the C2H4 selectivity exceeding 85%. This data confirms the economic feasibility of EASH in real-world applications. Furthermore, through in situ Raman spectroscopy and theoretical calculations, we elucidated the catalytic mechanism involving interfacial hydrogen spillover. Our findings underscore the economic viability and potential of EASH as a greener and scalable approach for C2H4 production, thus advancing the field of electrocatalysis in sustainable chemical synthesis.
The lifetime of hydroxyl radicals (â OH) in the fuel cell catalyst layer remains uncertain, which hampers the comprehension of radical-induced degradation mechanisms and the development of longevity strategies for proton-exchange membrane fuel cells (PEMFCs). In this study, we have precisely determined that the lifetime of â OH radicals can extend up to several seconds in realistic fuel cell catalyst layers. This finding reveals that â OH radicals are capable of carrying out long-range attacks spanning at least a few centimeters during PEMFCs operation. Such insights hold great potential for enhancing our understanding of radical-mediated fuel cell degradation processes and promoting the development of durable fuel cell devices.
OBJECTIVE: Isolated intra-articular anterior cruciate ligament (ACL) reconstruction is not capable of restoring instability in many cases leading some to recommend concomitant anterolateral ligament (ALL) reconstruction. The satisfactory fixation site and graft length change are crucial in ligament reconstruction to restore the ALL function and avoid some unwanted graft behavior. The purpose of this investigation is to determine the optimal isometric region on the anterolateral aspect of the knee for ALL reconstruction using a three-dimensional optical instrument and a suture similar to an intraoperative isometric test. METHODS: Six freshly frozen cadaveric human knees were used in this study. Data regarding the anterolateral surface were obtained using an optical measurement system to create a three-dimensional model. Nine points were selected on the femur (F1-F9) and tibia (Ta-Ti) respectively. The three-dimensional length change between each pair of tibial and femoral points was measured during passive knee flexion from 0° to 90° in 15° increments. Subsequently, five femoral points (A-E) were selected from the lateral femur, located in different areas relative to the lateral femoral epicondyle, and three tibial reference points (T1-T3) were selected in the isometric test. The changes in the length between each pair of reference points were measured using sutures. The 95% confidence interval for the rate of length change was estimated using the mean and standard deviation of the maximum rate of length change at different flexion angles, and the data were expressed as the mean (95% confidence interval) and compared with the maximum acceptable rate of change (10%). RESULTS: The maximum acceptable change rate for ligament reconstruction is 10%, and the mean maximum rates and the 95% confidence interval (CI) of length change for the point combinations were calculated. Among all the combined points measured using the optical measurement system and the suture, the qualified point combination for reconstruction was F3 (8mm posterior and 8mm proximal to the lateral femoral epicondyle)-Tb (8mm proximal to the midpoint between the center of Gerdy's tubercle and the fibula head), A (posterior and proximal to the lateral femoral epicondyle)-T2 (10mm below the joint line)and A-T3 (15 mm below the joint line). The position of F3-Tb and A-T2 are close to each other. CONCLUSION: The most isometric area of the femur for ALL reconstruction was posterior and proximal to the lateral femoral epicondyle. We recommend that the initial location of the femoral point be set at 8 mm posterior and 8 mm proximal to the lateral femoral epicondyle and the tibial point at approximately 10 mm below the joint line, midway between Gerdy's tubercle and fibular head, and subsequently adjusted to the most satisfactory position according to the isometric test.
Knee Joint , Tibia , Humans , Biomechanical Phenomena , Knee Joint/surgery , Tibia/surgery , Femur/surgery , Range of Motion, Articular , Cadaver , Ligaments
Electrochemical conversion of alkanes to high value-added oxygenated products under a mild condition is of significance. Herein, we effectively couple the electrocatalysis of H2 O2 with the thermo-catalysis of propane oxidation in the cathode of proton exchange membrane fuel cell. Specifically, H2 O2 is in-situ generated on the nitric acid-treated carbon black (C-acid) via 2e- process of oxygen reduction reaction, and then transports to the Fe active sites of MIL-53 (Al, Fe) metal-organic frameworks for propane oxidation. Based on this strategy, the space-time yield of C3 oxygenated products of propane oxidation reaches 2.65â µmol h-1 cm-2 , which represents a new benchmark for electrochemical alkane oxidation in the fuel-cell-type electrolyzer. This study highlights the importance of multifunctional composite catalysts in the field of electrosynthesis.
Demetalation, caused by the electrochemical dissolution of metal atoms, poses a significant challenge to the practical application of single-atom catalytic sites (SACSs) in proton exchange membrane-based energy technologies. One promising approach to inhibit SACS demetalation is the use of metallic particles to interact with SACSs. However, the mechanism underlying this stabilization remains unclear. In this study, we propose and validate a unified mechanism by which metal particles can inhibit the demetalation of Fe SACSs. Metal particles act as electron donors, decreasing the Fe oxidation state by increasing the electron density at the FeN4 position, thereby strengthening the Fe-N bond, and inhibiting electrochemical Fe dissolution. Different types, forms, and contents of metal particles increase the Fe-N bond strength to varying extents. A linear correlation between the Fe oxidation state, Fe-N bond strength, and electrochemical Fe dissolution amount supports this mechanism. Our screening of a particle-assisted Fe SACS led to a 78% reduction in Fe dissolution, enabling continuous operation for up to 430 h in a fuel cell. These findings contribute to the development of stable SACSs for energy applications.
The detailed structure of the water layer in the inner Helmholtz plane of a solid/aqueous solution interface is closely related to the electrochemical and catalytic performances of electrode materials. While the applied potential can have a great impact, specifically adsorbed species can also influence the interfacial water structure. With the specific adsorption of p-nitrobenzoic acid on the Au(111) surface, a protruding band above 3600 cm-1 appears in the electrochemical infrared spectra, indicating a distinct interfacial water structure as compared to that on bare metal surfaces, which displays a potential-dependent broad band in the range of 3400-3500 cm-1. Although three possible structures have been guessed for this protruding infrared band, the band assignment and interfacial water structure remain ambiguous in the past two decades. Herein, by combining surface-enhanced infrared absorption spectroscopy and our newly developed quantitative computational method for electrochemical infrared spectra, the protruding infrared band is clearly assigned to the surface-enhanced stretching mode of water molecules hydrogen-bonded to the adsorbed p-nitrobenzoate ions. Water molecules, meanwhile, are hydrogen-bonded with themselves to form chains of five-membered rings. Based on the reaction free energy diagram, we further demonstrate that both hydrogen-bonding interactions and coverages of specifically adsorbed p-nitrobenzoate play an important role in determining the structure of the water layer in the Au(111)/p-nitrobenzoic acid solution interface. Our work sheds light on structural studies of the inner Helmholtz plane under specific adsorptions, which advances the understanding of structure-property relationships in electrochemical and heterogeneous catalytic systems.
Lung adenocarcinoma (LUAD) is a malignant tumor with high mortality. At present, the clinicopathologic feature is the main breakthrough to assess the prognosis of LUAD patients. However, in most cases, the results are less than satisfactory. Cox regression analysis was conducted in this study to obtain methylation sites with significant prognostic relevance based on mRNA expression, DNA methylation data, and clinical data of LUAD from The Cancer Genome Atlas Program database. LUAD patients were grouped into 4 subtypes according to different methylation levels using K-means consensus cluster analysis. By survival analysis, patients were grouped into high-methylation and low-methylation groups. Later, 895 differentially expressed genes (DEGs) were obtained. Eight optimal methylation signature genes associated with prognosis were screened by Cox regression analysis, and a risk assessment model was constructed based on these genes. Samples were then classified into high-risk and low-risk groups depending on the risk assessment model, and prognostic, predictive ability was assessed using survival and receiver operating characteristic (ROC) curves. The results showed that this risk model had a great efficacy in predicting the prognosis of patients, and it was, therefore, able to be an independent prognostic factor. At last, the enrichment analysis demonstrated that the signaling pathways, including cell cycle, homologous recombination, P53 signaling pathway, DNA replication, pentose phosphate pathway, and glycolysis gluconeogenesis were remarkably activated in the high-risk group. In general, we construct an 8-gene model based on DNA methylation molecular subtypes by a series of bioinformatics methods, which can provide new insights for predicting the prognosis of patients with LUAD.
Adenocarcinoma of Lung , Lung Neoplasms , Humans , DNA Methylation , Cell Cycle , Cell Division
Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton transfer rate and then tune electrocatalytic performance. However, the mechanism for regulating proton transfer remains ambiguous. Here, we quantify the cation effect on proton diffusion in solution by hydrogen evolution on microelectrodes, revealing the rate can be suppressed by more than 10 times. Different from the prevalent opinions that proton transport is slowed down by modified electric field, we found water structure imposes a more evident effect on kinetics. FTIR test and path integral molecular dynamics simulation indicate that proton prefers to wander within the hydration shell of cations rather than to hop rapidly along water wires. Low connectivity of water networks disrupted by cations corrupts the fast-moving path in bulk water. This study highlights the promising way for regulating proton kinetics via a modified water structure.
Electroreduction of nitrate into ammonia (NRA) provides a sustainable route to convert the widespread nitrate pollutants into high-value-added products under ambient conditions, which unfortunately suffers from unsatisfactory selectivity due to the competitive hydrogen evolution reaction (HER). Previous strategies of modifying the metal sites of catalysts often met a dilemma for simultaneously promoting activity and selectivity toward NRA. Here, a general strategy is reported to enable an efficient and selective NRA process through coordination modulation of single-atom catalysts to tailor the local proton concentration at the catalyst surface. By contrast, two analogous Ni-single-atom enriched conjugated coordination polymers (NiO4 -CCP and NiN4 -CCP) with different coordination motifs are investigated for the proof-of-concept study. The NiO4 -CCP catalyst exhibits an ammonia yield rate as high as 1.83 mmol h-1 mg-1 with a Faradaic efficiency of 94.7% under a current density of 125 mA cm-2 , outperforming the NiN4 -CCP catalyst. These experimental and theoretical studies both suggest that the strategy of coordination modulation can not only accelerate the NRA by adjusting the adsorption energies of NRA intermediates on the metal sites but also inhibit the HER through regulating the proton migration with contributions from the metal-hydrated cations adsorbed at the catalyst surface, thus achieving simultaneous enhancement of NRA selectivity and activity.
OBJECTIVE: Arthroscopic release is effective for patients with shoulder stiffness, but the traditional inside-out procedure cannot effectively alleviate the mobility of some severe stiff shoulder and even cause itrogenic injuries sometimes. The aim of this study is to evaluate the clinical efficacy and advantages of a modified outside-in shoulder release approach for severe shoulder stiffness. METHODS: Included in this retrospective study were 15 patients (five male and 10 female) with severe shoulder stiffness who underwent modified outside-in shoulder release surgery at our hospital between June 2019 and March 2021. Of them, 10 patients had a primary frozen shoulder and five had secondary shoulder stiffness, involving the right shoulder in six cases and the left shoulder in nine cases. The mean age of the 15 patients was 56.7 (34-69) years. The patients were instructed to exercise passively from second-day post-operation and enhance the rehabilitation exercise gradually. All patients received a range of motion (ROM) examination before and after surgery. The American Shoulder and Elbow Surgeon's Score (ASES), Constant Score (CS), and Visual Analog Scale (VAS) score for pain were recorded. All data were tested by normal distribution first and then by paired T test, otherwise by Wilcoxon rank sum test. RESULTS: The mean follow-up period was 18.2 (12-33) months. Compared with the preoperative value, the mean ASES score at the final follow-up improved from 38.4 ± 7.37 to 88.13 ± 6.33 points; the mean CS score from 43.27 ± 6.71 to 78.74 ± 6.93 points; the mean VAS score from 5.07 ± 1.03 to 0.81 ± 0.83 points; forward flexion from 81.93° ± 11.45° to 156.73° ± 9.12°; abduction from 65.93° ± 16.82° to 144.80° ± 8.83°; neutral external rotation from 13.53° ± 10.38° to 51.20° ± 4.77°; internal rotation from the buttock to waist (L3), all showing a significant difference (P < 0.0001). No serious complication was observed in any patient during the postoperative follow-up periods. CONCLUSION: The present study has demonstrated that the modified arthroscopic outside-in shoulder release approach can improve ROM of patients and alleviate pain effectively, proving it to be an appropriate surgical option for the treatment of severe shoulder stiffness.
Joint Diseases , Shoulder Joint , Humans , Male , Female , Middle Aged , Aged , Shoulder , Retrospective Studies , Shoulder Joint/surgery , Arthroscopy/methods , Joint Capsule Release/methods , Treatment Outcome , Range of Motion, Articular
Partial-thickness rotator cuff tears are common diseases causing pain and disability. Among the different surgical methods, the transtendon repair technique is recommended due to its biomechanically superiority. However, this technique has a high learning curve and is time-consuming. In this Technical Note, we introduce a safer and more effective modified transtendon repair technique. Our switching-scope technique sets a switching stick into the glenohumeral joint through the posterior portal and is used as a guide for switching the arthroscope between the subacromial and articular spaces. This technique can reduce surgical time and overcome the disadvantage of vision limitation in articular-sided transtendon repair.
Interfacial pH is critical to electrocatalytic reactions involving proton-coupled electron transfer (PCET) processes, and maintaining an optimal interfacial pH at the electrochemical interface is required to achieve high activity. However, the interfacial pH varies inevitably during the electrochemical reaction owing to slow proton transfer at the interfacial layer, even in buffer solutions. It is therefore necessary to find an effective and general way to promote proton transfer for regulating the interfacial pH. In this study, we propose that promoting proton transfer at the interfacial layer can be used to regulate the interfacial pH in order to enhance electrocatalytic activity. By adsorbing a bifunctional 4-mercaptopyridine (4MPy) molecule onto the catalyst surface via its thiol group, the pyridyl group can be tethered on the electrochemical interface. The pyridyl group acts as both a good proton acceptor and donor for promoting proton transfer at the interfacial layer. Furthermore, the pK a of 4MPy can be modulated with the applied potentials to accommodate the large variation of interfacial pH under different current densities. By in situ electrochemical surface-enhanced Raman spectroscopy (in situ EC-SERS), we quantitatively demonstrate that proton transfer at the interfacial layer of the Pt catalyst coated with 4MPy (Pt@4MPy) remains ideally thermoneutral during the H+ releasing electrocatalytic oxidation reaction of formic acid (FAOR) at high current densities. Thus, the interfacial pH is controlled effectively. In this way, the FAOR apparent current measured from Pt@4MPy is twice that measured from a pristine Pt catalyst. This work establishes a general strategy for regulating interfacial pH to enhance the electrocatalytic activities.
The rational design of non-Pt oxygen reduction reaction (ORR) catalysts and catalyst layers in fuel cells is largely impeded by insufficient knowledge of triple-phase boundaries (TPBs) in the micropore and mesopore ranges. Here, we developed a size-sensitive molecular probe method to resolve the TPB of Fe/N/C catalyst layers in these size ranges. More than 70% of the ORR activity was found to be contributed by the 0.8- to 2.0-nanometer micropores of Fe/N/C catalysts, even at a low micropore area fraction of 29%. Acid-alkaline interactions at the catalyst-polyelectrolyte interface deactivate the active sites in mesopores and macropores, resulting in inactive TPBs, leaving micropores without the interaction as the active TPBs. The concept of active and inactive TPBs provides a previously unidentified design principle for non-Pt catalyst and catalyst layers in fuel cells.
Electrochemical conversion of propene is a promising technique for manufacturing commodity chemicals by using renewable electricity. To achieve this goal, we still need to develop high-performance electrocatalysts for propene electrooxidation, which highly relies on understanding the reaction mechanism at the molecular level. Although the propene oxidation mechanism has been well investigated at the solid/gas interface under thermocatalytic conditions, it still remains elusive at the solid/liquid interface under an electrochemical environment. Here, we report the mechanistic studies of propene electrooxidation on PdO/C and Pd/C catalysts, considering that the Pd-based catalyst is one of the most promising electrocatalytic systems. By electrochemical in situ attenuated total reflection Fourier transform infrared spectroscopy, a distinct reaction pathway was observed compared with conventional thermocatalysis, emphasizing that propene can be dehydrogenated at a potential higher than 0.80 V, and strongly adsorb via µ-CâCHCH3 and µ3-η2-CâCHCH3 configuration on PdO and Pd, respectively. The µ-CâCHCH3 is via bridge bonds on adjacent Pd and O atoms on PdO, and it can be further oxidized by directly taking surface oxygen from PdO, verified by the H218O isotope-edited experiment. A high surface oxygen content on PdO/C results in a 3 times higher turnover frequency than that on Pd/C for converting propene into propene glycol. This finding highlights the different reaction pathways under an electrochemical environment, which sheds light on designing next-generation electrocatalysts for propene electrooxidation.
A bicyclic pyrone-type species on oxygen-doped carbon catalysts was identified as the active site for the oxygen reduction reaction in acidic solution. It has much higher activity than that of typical nitrogen-doped carbon catalysts (0.219 e s-1 site-1vs. 0.021-0.088 e s-1 site-1 at 0.6 VRHE). The ortho-carbon atom in the carbonyl ring of the pyrone-type species was revealed as the reactive site by theoretical calculations.
Carbon , Pyrones , Carbon/chemistry , Catalytic Domain , Oxidation-Reduction , Oxygen/chemistry
The oxygen reduction reaction (ORR) activity of the Fe/N/Carbon catalysts derived from the pyrolysis of zeolitic-imidazolate-framework-8 (ZIF-8) has been still lower than that of commercial Pt-based catalysts utilized in the proton exchange membrane fuel cells (PEMFCs) due to low density of accessible active sites. In this study, an efficient carbon-supporting strategy is developed to enhance the ORR efficiency of the ZIF-derived Fe/N/Carbon catalysts by increasing the accessible active site density. The enhancement lies in (i) improving the accessibility of active sites via converting dodecahedral particles to graphene-like layered materials and (ii) enhancing the density of FeNx active sites via suppressing the formation of nanoparticles as well as providing extra spaces to host active sites. The optimized and efficient Fe/N/Carbon catalyst shows a half-wave potential (E1/2) of 0.834 V versus reversible hydrogen electrode in acidic media and produces a peak power density of 0.66 W cm-2 in an air-fed PEMFC at 2 bar backpressure, outperforming most previously reported Pt-free ORR catalysts. Finally, the general applicability of the carbon-supporting strategy is confirmed using five different commercial carbon blacks. This work provides an effective route to derive Fe/N/Carbon catalysts exhibiting a higher power density in PEMFCs.
CO poisoning of Pt-group metal catalysts is a long-standing problem, particularly for hydrogen oxidation reaction in proton exchange membrane fuel cells. Here, we report a catalyst of Ru oxide-coated Ru supported on TiO2 (Ru@RuO2/TiO2), which can tolerate 1-3% CO, enhanced by about 2 orders of magnitude over the classic PtRu/C catalyst, for hydrogen electrooxidation in a rotating disk electrode test. This catalyst can work stably in 1% CO/H2 for 50 h. About 20% of active sites can survive even in a pure CO environment. The high CO tolerance is not via a traditional bifunctional mechanism, i.e., oxide promoting CO oxidation, but rather via hydrous metal oxide shell blocking CO adsorption. An ab initio molecular dynamics (AIMD) simulation indicates that water confined in grain boundaries of the Ru oxide layer and Ru surface can suppress the diffusion and adsorption of CO. This oxide blocking layer approach opens a promising avenue for the design of high CO-tolerant electrocatalysts for fuel cells.
