Deciphering the Mechanisms of Photo-Enhanced Catalytic Activities in Plasmonic Pd-Au Heteromeric Nanozymes for Colorimetric Analysis.

The growing demand for highly active nanozymes in various fields has led to the development of several strategies to enhance their activity. Plasmonic enhancement, a strategy used in heterogenous catalysis, represents a promising strategy to boost the activity of nanozymes. Herein, Pd-Au heteromeric nanoparticles (Pd-Au dimers) with well-defined heterointerfaces have been explored as plasmonic nanozymes. As a model system, the Pd-Au dimers with integrated peroxidase (POD)-like activity and plasmonic activity are used to investigate the effect of plasmons on enhancing the activity of nanozymes under visible light irradiation. Mechanistic studies revealed that the generation of hot electron-hole pairs plays a dominant role in plasmonic effect, and it greatly enhances the decomposition of H2 O2 to the reactive oxygen species (ROS) intermediates (•OH, •O2 - and 1 O2 ), leading to elevated POD-like activity of the Pd-Au dimers. Finally, the Pd-Au dimers are applied in the plasmon-enhanced colorimetric method for the detection of alkaline phosphatase, exhibiting broad linear range and low detection limit. This study not only provides a straightforward approach for regulating nanozyme activity through plasmonic heterostructures but also sheds light on the mechanism of plasmon-enhanced catalysis of nanozymes.

Steering the Selective Production of Glycolic Acid by Electrocatalytic Oxidation of Ethylene Glycol with Nanoengineered PdBi-Based Heterodimers.

Heterodimers of metal nanocrystals (NCs) with tailored elemental distribution have emerged as promising candidates in the field of electrocatalysis, owing to their unique structures featuring heterogeneous interfaces with distinct components. Despite this, the rational synthesis of heterodimer NCs with similar elemental composition remains a formidable challenge, and their impact on electrocatalysis has remained largely elusive. In this study, Pd@Bi-PdBi heterodimer NCs are synthesized through an underpotential deposition (UPD)-directed growth pathway. In this pathway, the UPD of Bi promotes a Volmer-Weber growth mode, allowing for judicious modulation of core-satellite to heterodimer structures through careful control of supersaturation and growth kinetics. Significantly, the heterodimer NCs are employed in the electrocatalytic process of ethylene glycol (EG) with high activity and selectivity. Compared with pristine Pd octahedra and common PdBi alloy NC, the unique heterodimer structure of the Pd@Bi-PdBi heterodimer NCs endows them with the highest electrocatalytic performance of EG and the best selectivity (≈93%) in oxidizing EG to glycolic acid (GA). Taken together, this work not only heralds a new strategy for UPD-directed synthesis of bimetallic NCs, but also provides a new design paradigm for steering the selectivity of electrocatalysts.

Probing local charge transfer processes of Pt-Au heterodimers in plasmon-enhanced electrochemistry by CO stripping techniques.

CO-stripping experiments are employed as a highly structure-sensitive and in situ strategy to explore the mechanisms of plasmon-enhanced electrooxidation reactions. By using Pt-Au heterodimers as a model catalyst, the plasmon-induced current and potential changes on Pt and Au sites can be identified and explained.

Surface Topographical Engineering of Chiral Au Nanocrystals with Chiral Hot Spots for Plasmon-Enhanced Chiral Discrimination.

Surface roughness in chiral plasmonic nanostructures generates asymmetrical localized electromagnetic fields, which hold great promise for applications in chiral recognition, chiroptical spectroscopic sensing, and enantioselective photocatalysis. In this study, we develop a surface topographical engineering approach to precisely manipulate the surface structures of chiral Au nanocrystals. Through carefully controlling the amounts of l- or d-cystine (Cys) and the seed solution in the growth process, we successfully synthesize chiral Au nanocrystals with highly disordered, ordered, and less ordered wrinkled surfaces. An underlying principle governing the relationship between surface roughness, orderliness, and chiroptical response is also proposed. More importantly, the chiral ordered wrinkles on the surfaces of the nanocrystals generate asymmetrical localized electronic fields with enhanced intensity, which achieve excellent plasmon-enhanced chiral discrimination ability for penicillamine (Pen) enantiomers. This work offers exciting prospects for manipulating the surface structures of chiral nanocrystals and designing highly sensitive plasmon-enhanced enantioselective sensors with chiral hot spots.

Maneuvering the Peroxidase-Like Activity of Palladium-Based Nanozymes by Alloying with Oxophilic Bismuth for Biosensing.

Engineering the catalytic performance of nanozymes is of vital importance for their broad applications in biological analysis, cancer treatment, and environmental management. Herein, a strategy to boost the peroxidase-like activity of Pd-based nanozymes with oxophilic metallic bismuth (Bi) is demonstrated, which is based on the incorporation of oxophilic Bi in the Pd-based alloy nanocrystals (NCs). To synthesize PdBi alloy NCs, a seed-mediated method is employed with the assistance of underpotential deposition (UPD) of Bi on Pd. The strong interaction of Bi atoms with Pd surfaces favors the formation of alloy structures with controllable shapes and excellent monodispersity. More importantly, the PdBi NCs show excellent peroxidase-like activities compared with pristine Pd NCs. The structure-function correlations for the PdBi nanozymes are elucidated, and an indirect colorimetric method based on cascade reactions to determine alkaline phosphatase (ALP) is established. This method has good linear range, low detection limit, excellent selectivity, and anti-interference. Collectively, this work not only provides new insights for the design of high-efficiency nanozymes, expands the colorimetric sensing platform based on enzyme cascade reactions, but also represents a new example for UPD-directed synthesis of alloy NCs.

Metallic Heterostructures for Plasmon-Enhanced Electrocatalysis.

Metallic heterogeneous nanostructures with plasmonic functionality have attracted great attention in the field of plasmon-enhanced electrocatalysis, where surface plasmons produced under light excitation could facilitate the overall electrocatalytic performances. Owing to their controllability, multifunctionality, and complexity, heterogeneous metallic nanostructures take advantages of the properties from individual components and synergistic effects from adjacent components, thus may achieve remarkable electrocatalytic performances. This review highlights the state-of-the-art progress of the application of metallic heterostructures for plasmon-enhanced electrocatalysis. First, a brief introduction to plasmonic heterogeneous nanostructures is demonstrated. Then, fundamental principles of localized surface plasmon resonance and the underlying mechanisms of plasmonic heterogeneous nanostructures in catalysis are discussed. This is followed by a discussion of recent advances of plasmonic heterogeneous nanostructures in plasmon-enhanced electrocatalysis, in which the enhanced activity, selectivity, and stability are particularly emphasized. Finally, an outlook of remaining challenges and future opportunities for plasmonic heterogeneous nanomaterials and plasmon-related electrocatalysis is presented.

Unconventional-Phase Crystalline Materials Constructed from Multiscale Building Blocks.

Crystal phase, an intrinsic characteristic of crystalline materials, is one of the key parameters to determine their physicochemical properties. Recently, great progress has been made in the synthesis of nanomaterials with unconventional phases that are different from their thermodynamically stable bulk counterparts via various synthetic methods. A nanocrystalline material can also be viewed as an assembly of atoms with long-range order. When larger entities, such as nanoclusters, nanoparticles, and microparticles, are used as building blocks, supercrystalline materials with rich phases are obtained, some of which even have no analogues in the atomic and molecular crystals. The unconventional phases of nanocrystalline and supercrystalline materials endow them with distinctive properties as compared to their conventional counterparts. This Review highlights the state-of-the-art progress of nanocrystalline and supercrystalline materials with unconventional phases constructed from multiscale building blocks, including atoms, nanoclusters, spherical and anisotropic nanoparticles, and microparticles. Emerging strategies for engineering their crystal phases are introduced, with highlights on the governing parameters that are essential for the formation of unconventional phases. Phase-dependent properties and applications of nanocrystalline and supercrystalline materials are summarized. Finally, major challenges and opportunities in future research directions are proposed.

Preventive interventions for lateral ankle sprains: A systematic review and meta-analysis.

OBJECTIVE: To evaluate the effect of preventive interventions for lateral ankle sprain in the general population. DATA SOURCES: A search of PubMed, EMBASE, Cochrane CENTRAL, Medline, CINAHL, and ClinicalTrials.gov was conducted up to August 2022. REVIEW METHODS: Randomized controlled trials and prospective cohort studies that evaluated any interventions for preventing lateral ankle sprain were included. Two reviewers independently conducted the search, screening, and data extraction. The methodological quality of each study was assessed using the revised Cochrane risk-of-bias tool for randomized trials or using the Cochrane Risk Of Bias In Non-Randomized Studies tool for prospective cohort studies. RESULTS: Seventeen studies met the inclusion criteria. Proprioceptive training exhibited better effects on preventing future lateral ankle sprain compared with the control group (risk ratio = 0.59, p < 0.001), and a stronger preventive effect was observed in participants with a history of lateral ankle sprain in the subgroup analysis (risk ratio = 0.49, p = 0.02). Compared with no bracing, ankle bracing had no significant better effect in preventing lateral ankle sprain (risk ratio = 0.43, p = 0.05). Proprioceptive training and ankle bracing had similar preventive effects (risk ratio = 0.98, p = 0.97). Limited evidence hindered the synthesis of data on pain, swelling, costs, and time loss. CONCLUSION: Proprioceptive training is recommended for preventing lateral ankle sprain, especially for people with a history of lateral ankle sprain. Bracing seems to have an ambiguous preventive effect and requires more further investigation.

Characteristics of corticomuscular coupling during wheelchair Tai Chi in patients with spinal cord injury.

BACKGROUND: Wheelchair Tai Chi (WCTC) has been proved to have benefits for the brain and motor system of spinal cord injury (SCI) patients. However, the characteristics of corticomuscular coupling during WCTC are scarcely known. We aimed to investigate changes following SCI on corticomuscular coupling, and further compare the coupling characteristics of WCTC with aerobic exercise in SCI patients. METHODS: A total of 15 SCI patients and 25 healthy controls were recruited. The patients had to perform aerobic exercise and WCTC, while healthy controls needed to complete a set of WCTC. The participants accomplished the test following the tutorial video in a sitting position. The upper limb muscle activation was measured from upper trapezius, medial deltoid, biceps brachii and triceps brachii with surface electromyography. Cortical activity in the prefrontal cortex, premotor cortex, supplementary motor area and primary motor cortex was simultaneously collected by functional near-infrared spectroscopy. The functional connectivity, phase synchronization index and coherence values were then calculated and statistically analyzed. RESULTS: Compared to healthy controls, changes in functional connectivity and higher muscle activation were observed in the SCI group. There was no significant difference in phase synchronization between groups. Among patients, significantly higher coherence values between the left biceps brachii as well as the right triceps brachii and contralateral regions of interest were found during WCTC than during aerobic exercise. CONCLUSION: The patients may compensate for the lack of corticomuscular coupling by enhancing muscle activation. This study demonstrated the potential and advantages of WCTC in eliciting corticomuscular coupling, which may optimize rehabilitation following SCI.

Synthesis of Chiral Au Nanocrystals with Precise Homochiral Facets for Enantioselective Surface Chemistry.

Metal surfaces with intrinsic chirality play an irreplaceable role in many significant enantioselective chemical processes such as enantioselective catalysis, sensing, and separation. Nonetheless, current methods for the precise preparation of such chiral surfaces suffer with issues of unscalable production and low surface areas. Herein, we report the synthesis of chiral Au nanoparticles with precisely determined homochiral facets. Though a scalable wet chemical method, {125̅8}R and {85̅12}S high-Miller-index facets are obtained with the l- and d-chiral Au nanocrystals, respectively. The growth process of these homochiral facets is investigated, and a new nanocrystal growth pathway is revealed. More importantly, the remarkable enantioselective recognition properties of these homochiral surfaces are demonstrated and enable an efficient electrochemical method for chiral discrimination of l-/d-tryptophan. These results provide a foundation of fundamental studies of heterogeneous enantioselective processes and may pave way for the development of nanocatalysts for enantioselective chemistry.

Surface Molecular Functionalization of Unusual Phase Metal Nanomaterials for Highly Efficient Electrochemical Carbon Dioxide Reduction under Industry-Relevant Current Density.

The electrochemical carbon dioxide reduction reaction (CO2 RR) provides a sustainable strategy to relieve global warming and achieve carbon neutrality. However, the practical application of CO2 RR is still limited by the poor selectivity and low current density. Here, the surface molecular functionalization of unusual phase metal nanomaterials for high-performance CO2 RR under industry-relevant current density is reported. It is observed that 5-mercapto-1-methyltetrazole (MMT)-modified 4H/face-centered cubic (fcc) gold (Au) nanorods demonstrate greatly enhanced CO2 RR performance than original oleylamine (OAm)-capped 4H/fcc Au nanorods in both an H-type cell and flow cell. Significantly, MMT-modified 4H/fcc Au nanorods deliver an excellent carbon monoxide selectivity of 95.6% under the industry-relevant current density of 200 mA cm-2 . Density functional theory calculations reveal distinct electronic modulations by surface ligands, in which MMT improves while OAm suppresses the surface electroactivity of 4H/fcc Au nanorods. Furthermore, this method can be extended to various MMT derivatives and conventional fcc Au nanostructures in boosting CO2 RR performance.

Designer Gold-Framed Palladium Nanocubes for Plasmon-Enhanced Electrocatalytic Oxidation of Ethanol.

Surface plasmon of coinage metal nanostructures has been employed as a powerful route in boosting the performances in heterogenous catalysis. Development of efficient plasmonic nanocatalysts with high catalytic performance and efficient light harvesting properties is of vital importance. Herein, we rationally designed and synthesized a plasmonic nanocatalyst composed of Au-framed Pd nanocubes by an Ag(I)-assisted seed-mediated growth method. In the synthesis, the incorporation of Ag(I) suppresses the reduction of Au on the {100} surface of cubic Pd seeds and leads to the formation of Au nanoframes on the Pd nanocubes. The unique Au-framed Pd nanocubes can integrate the superior electrocatalytic of Pd and the outstanding plasmonic properties of Au. Thus, these nanostructures were employed as plasmonic nanocatalysts for plasmon-enhanced electrocatalytic oxidation of ethanol with improved stability.

Selective Epitaxial Growth of Rh Nanorods on 2H/fcc Heterophase Au Nanosheets to Form 1D/2D Rh-Au Heterostructures for Highly Efficient Hydrogen Evolution.

Phase engineering of nanomaterials (PEN) enables the preparation of metal nanomaterials with unconventional phases that are different from their thermodynamically stable counterparts. These unconventional-phase nanomaterials can serve as templates to construct precisely controlled metallic heterostructures for wide applications. Nevertheless, how the unconventional phase of templates affects the nucleation and growth of secondary metals still requires systematic explorations. Here, two-dimensional (2D) square-like Au nanosheets with an unconventional 2H/face-centered cubic (fcc) heterophase, composing of two pairs of opposite edges with 2H/fcc heterophase and fcc phase, respectively, and two 2H/fcc heterophase basal planes, are prepared and then used as templates to grow one-dimensional (1D) Rh nanorods. The effect of different phases in different regions of the Au templates on the overgrowth of Rh nanorods has been systematically investigated. By tuning the reaction conditions, three types of 1D/2D Rh-Au heterostructures are prepared. In the type A heterostructure, Rh nanorods only grow on the fcc defects including stacking faults and/or twin boundaries (denoted as fcc-SF/T) and 2H phases in two 2H/fcc edges of the Au nanosheet. In the type B heterostructure, Rh nanorods grow on the fcc-SF/T and 2H phases in two 2H/fcc edges and two 2H/fcc basal planes of the Au nanosheet. In the type C heterostructure, Rh nanorods grow on four edges and two basal planes of the Au nanosheet. Furthermore, the type C heterostructure shows promising performance toward the electrochemical hydrogen evolution reaction (HER) in acidic media, which is among the best reported Rh-based and other noble-metal-based HER electrocatalysts.

Unveiling the Actual Catalytic Sites in Nanozyme-Catalyzed Oxidation of o-Phenylenediamine.

Nanozymes have offered remarkable advantages over natural enzymes and found widespread applications including biosensors, immunoassays, nanomedicines, and environmental remediation. Oxidation of o-phenylenediamine (OPD) by nanozymes has been listed as a standard protocol for determining nanozyme activities. Given the complexity of OPD oxidation processes, however, the mechanism of nanozyme-catalyzed oxidation of OPD remains elusive. In this report, mechanistic studies of nanozyme-catalyzed oxidation of OPD are performed and a distinguishably different mechanism from that of natural enzymes is found. A combination of Fourier transform infrared spectroscopy, nuclear magnetic resonance, electrospray ionization mass spectrometry, and electron microscopic studies provides compelling evidence that polymerization of OPD occurs on the surface of several different nanozymes. The unexpected polymerization causes a dense coating layer of poly(o-phenylenediamine) (POPD) on nanozymes renders the intrinsic properties of nanozymes. Therefore, this fundamental discovery raise serious concerns using OPD-based colorimetric method for determining nanozyme activities. Without examining the surface change of nanozymes after catalytic reactions, the use of OPD-based colorimetric method for determining nanozyme activities is strongly discouraged. Furthermore, POPD is discovered as a new oxidase mimic, and this new mechanism also provides a general and robust method to coat nanomaterials with POPD polymers of enzyme-mimicking properties.

[Biomechanical analysis of ankle-foot complex during a typical Tai Chi movement-Brush Knee and Twist Step].

The purpose of this study is to analyze the biomechanics of ankle cartilage and ligaments during a typical Tai Chi movement-Brush Knee and Twist Step (BKTS). The kinematic and kinetic data were acquired in one experienced male Tai Chi practitioner while performing BKTS and in normal walking. The measured parameters were used as loading and boundary conditions for further finite element analysis. This study showed that the contact stress of the ankle joint during BKTS was generally less than that during walking. However, the maximum tensile force of the anterior talofibular ligament, the calcaneofibular ligament and the posterior talofibular ligament during BKTS was 130 N, 169 N and 89 N, respectively, while it was only 57 N, 119 N and 48 N during walking. Therefore, patients with arthritis of the ankle can properly practice Tai Chi. Practitioners with sprained lateral ligaments of the ankle joint were suggested to properly reduce the ankle movement range during BKTS.

Ethylene Selectivity in Electrocatalytic CO2 Reduction on Cu Nanomaterials: A Crystal Phase-Dependent Study.

The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO2 reduction reaction (CO2RR) to produce high-value hydrocarbons. However, studies to date are limited to the conventional face-centered cubic (fcc) Cu. Here, we report a crystal phase-dependent catalytic behavior of Cu, after the successful synthesis of high-purity 4H Cu and heterophase 4H/fcc Cu using the 4H and 4H/fcc Au as templates, respectively. Remarkably, the obtained unconventional crystal structures of Cu exhibit enhanced overall activity and higher ethylene (C2H4) selectivity in CO2RR compared to the fcc Cu. Density functional theory calculations suggest that the 4H phase and 4H/fcc interface of Cu favor the C2H4 formation pathway compared to the fcc Cu, leading to the crystal phase-dependent C2H4 selectivity. This study demonstrates the importance of crystal phase engineering of metal nanocatalysts for electrocatalytic reactions, offering a new strategy to prepare novel catalysts with unconventional phases for various applications.

Two-Dimensional Metal Nanomaterials: Synthesis, Properties, and Applications.

As one unique group of two-dimensional (2D) nanomaterials, 2D metal nanomaterials have drawn increasing attention owing to their intriguing physiochemical properties and broad range of promising applications. In this Review, we briefly introduce the general synthetic strategies applied to 2D metal nanomaterials, followed by describing in detail the various synthetic methods classified in two categories, i.e. bottom-up methods and top-down methods. After introducing the unique physical and chemical properties of 2D metal nanomaterials, the potential applications of 2D metal nanomaterials in catalysis, surface enhanced Raman scattering, sensing, bioimaging, solar cells, and photothermal therapy are discussed in detail. Finally, the challenges and opportunities in this promising research area are proposed.

Tai Chi Is Safe and Effective for the Hip Joint: A Biomechanical Perspective.

There is little research related to the biomechanical effects of Tai Chi on the hip joint. This study was aimed to analyze the biomechanical characteristic of a typical Tai Chi movement, Brush Knee and Twist Step. A total of 12 experienced older men voluntarily participated in this study. Each participant was requested to perform standard Brush Knee and Twist Step and normal walking. The scaled-generic musculoskeletal model of each participant was developed. A finite element model of the hip joint and pelvis was established and validated. Data from each trail were input to the model for simulation, and the biomechanics were compared between Brush Knee and Twist Step and walking. Compared with walking, Tai Chi may have better improvement in the range of motion of the hip joint and the coordination of the neuromuscular system under safer condition. It is suitable for patients with hip osteoarthritis and the older adults with severe muscle loss, and clinical studies are required to confirm it further.

Influence of Shoulder Position on Functional Control Ratio During Isokinetic Assessment.

CONTEXT: One of the possible mechanisms leading to secondary impingement syndrome may be the strength imbalance of shoulder rotators which is known as functional control ratio (FCR). The FCR is a ratio dividing the eccentric peak torque of the external rotators by the concentric peak torque of the internal rotators. Previous studies have focused on the reproducibility and reliability of isokinetic assessment, but there is little information on the influence of variable shoulder positions on FCR. OBJECTIVE: To compare shoulder FCR across 3 different shoulder abduction positions during isokinetic assessment. DESIGN: Cross-sectional study. SETTING: Biomechanics laboratory. PARTICIPANTS: Thirty-one healthy young university students (age 22.35 [0.95] y, weight 60.52 [9.31] kg, height 168.23 [9.47] cm). INTERVENTIONS: The concentric peak torque of internal rotators and eccentric peak torque of external rotators of right shoulder were measured on an isokinetic dynamometer. MAIN OUTCOME MEASURES: Concentric peak torque of the internal rotators and eccentric peak torque of the external rotators, measured using an isokinetic dynamometer. RESULTS: The concentric peak torque of internal rotators was significantly lower at 120° shoulder abduction compared with other positions (P < .001). The FCR was significantly higher at 120° shoulder abduction than 90° (P = .002) or 60° (P < .001) shoulder abduction because of the lower concentric peak torque. No significant difference was found in the FCR between the other 2 shoulder positions (P = .14). CONCLUSIONS: Shoulder position variations may influence FCR because of weakness of the internal rotators. Rehabilitation and injury prevention training programs should specifically focus on strengthening the internal rotators at more elevated angles of shoulder abduction.

Highly Excavated Octahedral Nanostructures Integrated from Ultrathin Mesoporous PtCu3 Nanosheets: Construction of Three-Dimensional Open Surfaces for Enhanced Electrocatalysis.

Developing electrocatalysts with ultrathin nanostructures and high mesoporosity is a relevant high-priority research direction toward enhancing the performance of noble metals. Herein, mesoporous, highly excavated octahedral PtCu3 nanostructures are prepared by a facile one-pot synthesis. The mesoporous, highly excavated octahedral PtCu3 nanostructures are built with mutually perpendicular interlaced mesoporous nanosheets with a thickness of ≈4.5 nm. Benefiting from its mesoporous features, three-dimensional (3D) open surfaces, ultrathin nanosheets, and a Cu-rich surface, PtCu3 exhibits excellent electrocatalytic performance and high antipoisoning activity toward the methanol oxidation reaction.