Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts.

Metal-catalysed reactions are often hypothesized to proceed on bifunctional active sites, whereby colocalized reactive species facilitate distinct elementary steps in a catalytic cycle1-8. Bifunctional active sites have been established on homogeneous binuclear organometallic catalysts9-11. Empirical evidence exists for bifunctional active sites on supported metal catalysts, for example, at metal-oxide support interfaces2,6,7,12. However, elucidating bifunctional reaction mechanisms on supported metal catalysts is challenging due to the distribution of potential active-site structures, their dynamic reconstruction and required non-mean-field kinetic descriptions7,12,13. We overcome these limitations by synthesizing supported, atomically dispersed rhodium-tungsten oxide (Rh-WOx) pair site catalysts. The relative simplicity of the pair site structure and sufficient description by mean-field modelling enable correlation of the experimental kinetics with first principles-based microkinetic simulations. The Rh-WOx pair sites catalyse ethylene hydroformylation through a bifunctional mechanism involving Rh-assisted WOx reduction, transfer of ethylene from WOx to Rh and H2 dissociation at the Rh-WOx interface. The pair sites exhibited >95% selectivity at a product formation rate of 0.1 gpropanal cm-3 h-1 in gas-phase ethylene hydroformylation. Our results demonstrate that oxide-supported pair sites can enable bifunctional reaction mechanisms with high activity and selectivity for reactions that are performed in industry using homogeneous catalysts.

Stability-limiting heterointerfaces of perovskite photovoltaics.

Optoelectronic devices consist of heterointerfaces formed between dissimilar semiconducting materials. The relative energy-level alignment between contacting semiconductors determinately affects the heterointerface charge injection and extraction dynamics. For perovskite solar cells (PSCs), the heterointerface between the top perovskite surface and a charge-transporting material is often treated for defect passivation1-4 to improve the PSC stability and performance. However, such surface treatments can also affect the heterointerface energetics1. Here we show that surface treatments may induce a negative work function shift (that is, more n-type), which activates halide migration to aggravate PSC instability. Therefore, despite the beneficial effects of surface passivation, this detrimental side effect limits the maximum stability improvement attainable for PSCs treated in this way. This trade-off between the beneficial and detrimental effects should guide further work on improving PSC stability via surface treatments.

Exceptional electronic transport and quantum oscillations in thin bismuth crystals grown inside van der Waals materials.

Confining materials to two-dimensional forms changes the behaviour of the electrons and enables the creation of new devices. However, most materials are challenging to produce as uniform, thin crystals. Here we present a synthesis approach where thin crystals are grown in a nanoscale mould defined by atomically flat van der Waals (vdW) materials. By heating and compressing bismuth in a vdW mould made of hexagonal boron nitride, we grow ultraflat bismuth crystals less than 10 nm thick. Due to quantum confinement, the bismuth bulk states are gapped, isolating intrinsic Rashba surface states for transport studies. The vdW-moulded bismuth shows exceptional electronic transport, enabling the observation of Shubnikov-de Haas quantum oscillations originating from the (111) surface state Landau levels. By measuring the gate-dependent magnetoresistance, we observe multi-carrier quantum oscillations and Landau level splitting, with features originating from both the top and bottom surfaces. Our vdW mould growth technique establishes a platform for electronic studies and control of bismuth's Rashba surface states and topological boundary modes1-3. Beyond bismuth, the vdW-moulding approach provides a low-cost way to synthesize ultrathin crystals and directly integrate them into a vdW heterostructure.

The SRCAP chromatin remodeling complex promotes oxidative metabolism during prenatal heart development.

Mammalian heart development relies on cardiomyocyte mitochondrial maturation and metabolism. Embryonic cardiomyocytes make a metabolic shift from anaerobic glycolysis to oxidative metabolism by mid-gestation. VHL-HIF signaling favors anaerobic glycolysis but this process subsides by E14.5. Meanwhile, oxidative metabolism becomes activated but its regulation is largely elusive. Here, we first pinpointed a crucial temporal window for mitochondrial maturation and metabolic shift, and uncovered the pivotal role of the SRCAP chromatin remodeling complex in these processes in mouse. Disruption of this complex massively suppressed the transcription of key genes required for the tricarboxylic acid cycle, fatty acid ß-oxidation and ubiquinone biosynthesis, and destroyed respirasome stability. Furthermore, we found that the SRCAP complex functioned through H2A.Z deposition to activate transcription of metabolic genes. These findings have unveiled the important physiological functions of the SRCAP complex in regulating mitochondrial maturation and promoting oxidative metabolism during heart development, and shed new light on the transcriptional regulation of ubiquinone biosynthesis.

Elucidating Phase Transformation and Surface Amorphization of Li7 La3 Zr2 O12 by In Situ Heating TEM.

Garnet-type Li7 La3 Zr2 O12 (LLZO) solid-state electrolytes hold great promise for the next-generation all-solid-state batteries. An in-depth understanding of the phase transformation during synthetic processes is required for better control of the crystallinity and improvement of the ionic conductivity of LLZO. Herein, the phase transformation pathways and the associated surface amorphization are comparatively investigated during the sol-gel and solid-state syntheses of LLZO using in situ heating transmission electron microscopy (TEM). The combined ex situ X-ray diffraction and in situ TEM techniques are used to reveal two distinct phase transformation pathways (precursors â†’ La2 Zr2 O7  â†’ LLZO and precursors â†’ LLZO) and the subsequent layer-by-layer crystal growth of LLZO on the atomic scale. It is also demonstrated that the surface amorphization surrounding the LLZO crystals is sensitive to the postsynthesis cooling rate and significantly affects the ionic conductivity of pelletized LLZO. This work brings up a critical but often overlooked issue that may greatly exacerbate the Li-ion conductivity by undesired synthetic conditions, which can be leveraged to ameliorate the overall crystallinity to improve the electrochemical performance of LLZO. These findings also shed light on the significance of optimizing surface structure to ensure superior performance of Li-ion conductors.

Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction.

In analogy to natural enzymes, an elaborated design of catalytic systems with a specifically tailored local chemical environment could substantially improve reaction kinetics, effectively combat catalyst poisoning effect and boost catalyst lifetime under unfavourable reaction conditions. Here we report a unique design of 'Ni(OH)2-clothed Pt-tetrapods' with an amorphous Ni(OH)2 shell as a water dissociation catalyst and a proton conductive encapsulation layer to isolate the Pt core from bulk alkaline electrolyte while ensuring efficient proton supply to the active Pt sites. This design creates a favourable local chemical environment to result in acidic-like hydrogen evolution reaction kinetics with a lowest Tafel slope of 27 mV per decade and a record-high specific activity and mass activity in alkaline electrolyte. The proton conductive Ni(OH)2 shell can also effectively reject impurity ions and retard the Oswald ripening, endowing a high tolerance to solution impurities and exceptional long-term durability that is difficult to achieve in the naked Pt catalysts. The markedly improved hydrogen evolution reaction activity and durability in an alkaline medium promise an attractive catalyst material for alkaline water electrolysers and renewable chemical fuel generation.

Cartilage-Inspired, High-Strength, and Heat-Tolerant Lubricating Hydrogels by Macrophase Separation.

Hydrogels are considered as a potential cartilage replacement material based on their structure being similar to natural cartilage, which are of great significance in repairing cartilage defects. However, it is difficult for the existing hydrogels to combine the high load bearing and low friction properties (37 °C) of cartilage through sample methods. Herein, we report a facile and new fabrication strategy to construct the PNIPAm/EYL hydrogel by using the macrophase separation of supersaturated N-isopropylacrylamide (NIPAm) monomer solution to promote the formation of liposomes from egg yolk lecithin (EYL) and asymmetric template method. The PNIPAm/EYL hydrogels possess a relatively high compressive strength (more than 12 MPa), fracture energy (9820 J/m2), good fatigue resistance, lubricating properties, and excellent biocompatibility. Compared with the PNIPAm hydrogel, the friction coefficient (COF 0.046) of PNIPAm/EYL hydrogel is reduced by 50%. More importantly, the COF (0.056) of PNIPAm/EYL hydrogel above lower critical solution temperature (LCST) does not increase significantly, exhibiting heat-tolerant lubricity. The finite element analysis further proves that PNIPAm/EYL hydrogel can effectively disperse the applied stress and dissipate energy under load conditions. This work not only provides new insights for the design of high-strength lubricating hydrogels but also lays a foundation for the treatment of cartilage injury as a substitute material.

Periodic Assembly of Diblock Pt-Au Heteronanowires for the Methanol Oxidation Reaction.

Periodic assembly of heterogeneous nanoparticles provides a strategy for integrating distinct nanocatalyst blocks where their synergic effects can be explored for diverse applications. To achieve the synergistic enhancement, an intimate clean interface is preferred which however is usually plagued by the bulky surfactant molecules used in the synthesis and assembly process. Herein, we showed the creation of one-dimensional Pt-Au nanowires (NWs) with periodic alternating Pt and Au nanoblocks, by assembling Pt-Au Janus nanoparticles with the assistance of peptide T7 (Ac-TLTTLTN-CONH2). It is demonstrated that the Pt-Au NWs showed much-improved performance in the methanol oxidation reaction (MOR), exhibiting 5.3 times higher specific activity and 2.5 times higher mass activity than the current state-of-the-art commercial Pt/C catalyst. In addition, the periodic heterostructure also improves the stability of Pt-Au NWs in the MOR, where the Pt-Au NWs retained 93.9% of their initial mass activity much higher than commercial Pt/C (30.6%).

Two-Dimensional Fe-N-C Single-Atomic-Site Catalysts with Boosted Peroxidase-Like Activity for a Sensitive Immunoassay.

Single-atomic-site catalysts (SASCs) with peroxidase (POD)-like activities have been widely used in various sensing platforms, like the enzyme-linked immunosorbent assay (ELISA). Herein, a two-dimensional Fe-N-C-based SASC (2D Fe-SASC) is successfully synthesized with excellent POD-like activity (specific activity = 90.11 U/mg) and is used to design the ELISA for herbicide detection. The 2D structure of Fe-SASC enables the exposure of numerous single atomic active sites on the surface as well as boosts the POD-like activity, thereby enhancing the sensing performance. 2D Fe-SASC is assembled into competitive ELISA kit, which achieves an excellent detection performance for 2,4-dichlorophenoxyacetic acid (2,4-D). Fe-SASC has great potential in replacing high-cost natural enzymes and working on various advanced sensing platforms with high sensitivity for the detection of various target biomarkers.

Suppressing ion migration in metal halide perovskite via interstitial doping with a trace amount of multivalent cations.

Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote the performance and stability of perovskite optoelectronics. However, such interstitial doping inevitably leads to lattice microstrain that impairs the long-range ordering and stability of the crystals, causing a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with a reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). The photovoltaic performances and operational stability of the prototypical perovskite solar cells are enhanced with a trace amount of Nd3+ doping while minimizing the sacrificial trade-off.

Asymptomatic Gluteal Tendinosis Does Not Adversely Affect Outcomes of Primary Total Hip Arthroplasty.

BACKGROUND: The aim of this study was to compare outcomes after total hip arthroplasty (THA) in patients who have preoperative asymptomatic gluteal tendinosis (aGT) to a control group with no gluteal tendinosis (GT). METHODS: A retrospective analysis was performed using data from patients who underwent THA between March 2016 and October 2020. An aGT was diagnosed using hip magnetic resonance imaging (MRI) without clinical symptoms. Patients who had aGT were matched (1:1) to patients without GT on MRI. A total of 56 aGT hips and 56 hips without GT were found using propensity-score matching. Patient-reported outcomes, intraoperative macroscopic evaluation, outcome measurements, postoperative physical examinations, complications, and revisions were compared for both groups. RESULTS: When compared to preoperative outcomes, both groups demonstrated significant improvements in patients-reported outcomes at the final follow-up. There were no significant differences between both groups for preoperative scores, 2-year postoperative outcome scores, or the magnitude of improvement. Patients in the aGT group were significantly less likely to obtain the MCID for the SF-36 MCS score (50.2 versus 69.3%, P = .034). However, there were no other differences in the rates of meeting the MCID between both groups. The aGT group demonstrated significantly higher rates of partial tendon degeneration of the gluteus medius muscle. CONCLUSION: Asymptomatic gluteal tendinosis patients who have osteoarthritis and undergo THA may expect favorable patients-reported outcomes at minimum 2-year follow-up. These results were comparable with those of a control group of patients without gluteal tendinosis. LEVEL OF EVIDENCE: III.

Effectiveness of Arthroscopically Assisted Surgery for Ankle Arthrodesis.

Regarding the treatment of ankle arthritis, the choice of arthroscopic ankle arthrodesis (AAA) or open ankle arthrodesis (OAA) remains controversial. To guide clinical decision-making, we conducted a meta-analysis on the optimal treatment of ankle arthrodesis. We identified eligible studies published from June 1, 1969 to June 1, 2020 using the Cochrane Library, PubMed, OVID, Embase, and Medline searched the references of relevant studies. Randomized and non-randomized studies that compared outcomes of AAA and OAA were included. After the methodologic assessment, available data were extracted and statistically reviewed. The primary outcomes were overall complications rate, tourniquet time, length of the hospital stay, non-union rate, and rate to fusion. The secondary outcomes were delayed union and postoperative infection rate. We included 9 studies comparing arthroscopic and open in patients with ankle arthrodesis, comprising 467 participants. AAA had the advantage of demonstrating a lower overall complication rate (odds ratio [OR], 0.44 [95% confidence interval [CI], 0.26-0.73]; p = .002), shorter intraoperative tourniquet time (mean difference [MD], -16.49 [95% CI, -23.51 to -9.46]; p < .001), shorter length of the hospital stay (MD -1.75, 95% CI -1.94 to -1.2, p < .001),lower non-union rate (OR, -0.07 [95% CI, -0.13 to -0.02]; p <.01) and higher rate to fusion (OR, 4.2 [95% CI, 1.96-8.99]; p < .001) in comparison with OAA. Yet, no significant differences were found in delayed union (OR, 0.46 [95% CI, 0.10-2.04]; p = .30) and postoperative infection rate (OR, 0.45 [95% CI, 0.17-1.15]; p = .09) between the groups. Our results suggest that arthroscopic ankle arthrodesis is superior to open ankle arthrodesis alone in the treatment of ankle arthritis based on the overall complication rate, intraoperative tourniquet time, length of the hospital stay, non-union rate and rate to fusion. However, further high-quality randomized controlled trials with appropriate blinding methods are needed to confirm the findings.

Teaching PCR for Simultaneous Sensing of Gene Transcription and Downstream Metabolites by Cucurbit[8]uril-Mediated Intervention of Polymerase Activity.

The target of typical PCR analysis is restricted to nucleic acids. To this end, we report here a novel strategy to simultaneously detect genetic and metabolic markers using commercial PCR kits with cucurbit[8]urils (CB[8]) implemented to manipulate the activity of Taq DNA polymerase. CB[8] binds with the nonionic surfactants and displaces them from the polymerase surface, resulting in decreased enzyme activity. Meanwhile, the inhibited enzyme can be reversibly activated when spermine, the downstream metabolite of ornithine decarboxylase (ODC), is present in the sample, which competitively binds to CB[8] and recovers polymerase activity. CB[8] was implemented in conventional PCR kits not only to reduce false-positive results but also to extend the detection range of PCR technology. With this novel method to detect ODC in cell lysates containing both the nucleotides and intracellular metabolites, positive results were only observed in highly active HEK 293T cells, whereas silent cells treated with ODC inhibitor showed negative readouts, therefore providing a simple but elegant dual-modality PCR method for precision diagnosis.

Antifungal Volatile Organic Compounds from Streptomyces setonii WY228 Control Black Spot Disease of Sweet Potato.

Volatile organic compounds (VOCs) produced by microorganisms are considered promising environmental-safety fumigants for controlling postharvest diseases. Ceratocystis fimbriata, the pathogen of black spot disease, seriously affects the quality and yield of sweet potato in the field and postharvest. This study tested the effects of VOCs produced by Streptomyces setonii WY228 on the control of C. fimbriata in vitro and in vivo. The VOCs exhibited strong antifungal activity and significantly inhibited the growth of C. fimbriata. During the 20-day storage, VOC fumigation significantly controlled the occurrence of the pathogen, increased the content of antioxidants and defense-related enzymes and flavonoids, and boosted the starch content so as to maintain the quality of the sweet potatoes. Headspace analysis showed that the volatiles 2-ethyl-5-methylpyrazine and dimethyl disulfide significantly inhibited the mycelial growth and spore germination of C. fimbriata in a dose-dependent manner. Fumigation with 100 µL/L 2-ethyl-5-methylpyrazine completely controlled the pathogen in vivo after 10 days of storage. Transcriptome analysis showed that volatiles mainly downregulated the ribosomal synthesis genes and activated the proteasome system of the pathogen in response to VOC stress, while the genes related to spore development, cell membrane synthesis, mitochondrial function, and hydrolase and toxin synthesis were also downregulated, indicating that WY228-produced VOCs have diverse modes of action for pathogen control. Our study demonstrates that fumigation of sweet potato tuberous roots with S. setonii WY228 or use of formulations based on the VOCs is a promising new strategy to control sweet potato and other food and fruit pathogens during storage and shipment. IMPORTANCE Black spot disease caused by Ceratocystis fimbriata has caused huge economic losses to worldwide sweet potato production. At present, the control of C. fimbriata mainly depends on toxic fungicides, and there is a lack of effective alternative strategies. The research on biological control of sweet potato black spot disease is also very limited. An efficient biocontrol technique against pathogens using microbial volatile organic compounds could be an alternative method to control this disease. Our study revealed the significant biological control effect of volatile organic compounds of Streptomyces setonii WY228 on black spot disease of postharvest sweet potato and the complex antifungal mechanism against C. fimbriata. Our data demonstrated that Streptomyces setonii WY228 and its volatile 2-ethyl-5-methylpyrazine could be a candidate strain and compound for the creation of fumigants and showed the important potential of biotechnology applications in the field of food and agriculture.

Label-free tumor cell screening based on IDO1-mediated tryptophan metabolism at single cell level.

Indoleamine 2,3-dioxygenase 1 (IDO1) plays a critical role in inflammatory and immunometabolism programming through catalyzing the oxidation of tryptophan (Trp) into downstream N-formylkynurenine. IDO1 is typically up-regulated in malignant tumors, making it a potential biomarker for cancer diagnosis. Here we show an effective strategy for tumor cell detection by integrating IDO1 activity assay with single cell-encapsulated droplets on a microfluidic platform for high-throughput bioanalysis. Mixed cells, as well as other cofactors, are encapsulated in individual droplets, which act as dynamic microreactors for IDO1-catalyzed oxidation of Trp. After pico-injection of a biosensing ensemble consisting of the macrocycle cucurbit [8]uril (Q8) and a fluorescent guest, rapid and robust screening of tumor cells by fluorescence signal is achieved in a few minutes reporting to Trp depletion, expanding the scope of conventional antibody-based detection of protein biomarkers. The results represent the first example of quantifying IDO1 enzymatic activity at the single cell level with a high-throughput performance, therefore promising warning signs and early diagnosis of tumor cells.

Pt3Co/Co Composite Catalysts on Porous N-Doped Carbon Support Derived from ZIF-67 with Enhanced HER and ORR Activities.

The primary challenge for efficient H2 evolution and hydrogen energy conversion is to develop highly active and stable catalysts with simple and reliable preparation processes. In this regard, we have designed and synthesized a porous carbon-supported low-Pt alloy catalyst (Pt3Co/Co@C composite) using ZIF-67 as a template. It showed uniformly dispersed Pt3Co/Co on the porous carbon layer due to the confinement effect of the porous carbon layer. Pt3Co/Co@C demonstrated excellent activity for the hydrogen evolution reaction in the full pH range, with an overpotential of 187 mV in 0.5 M H2SO4 to attain 100 mA/cm2 as well as long-term stability. It also displayed superior mass activity for the oxygen reduction reaction (ORR) at 0.85 V (vs RHE) compared to the commercial Pt/C. Furthermore, the Pt3Co/Co@C catalyst exclusively enabled a four-electron reaction process under ORR conditions without the competitive pathway to H2O2. The current work provides guidance for the design and facile synthesis of Pt-based catalysts with enhanced performance.

Abundant and diverse endophytic bacteria associated with medicinal plant Arctium lappa L. and their potential for host plant growth promoting.

Arctium lappa L. is one of the medicinal and food homologous plants in China, which is rich in nutrients and medicinal ingredients. The use of plant growth-promoting (PGP) endophytic bacteria is an alternative to reducing chemical fertilizers in agricultural production. The aim of this study was to analyze the diversity of endophytic bacteria in different cultivars of A. lappa L. collected from two geographical locations in China and evaluate PGP traits of the isolates and their potential PGP ability in greenhouse condition. Endophytic bacterial community was investigated by culture-dependent and culture-independent methods. Isolates were screened and investigated for multiple PGP traits, and representative strains were inoculated host seedlings to evaluate the growth promoting effect. A total of 348 endophytic bacteria were obtained and they were distributed into 4 phyla and 30 genera. In addition, high throughput sequencing revealed more abundant bacterial community, including 17 bacterial phyla and 207 genera. A high proportion of PGP traits were detected, including production of indole acetic acid, siderophore, ammonia and phosphate solubilization. Four representative strains with multiple PGP traits of the most dominant genera (Bacillus, Pantoea, Microbacterium and Pseudomonas) were further selected for host inoculation and growth promoting evaluation, and they significantly increase seedlings length, root length and fresh weight. This study demonstrated that A. lappa L. harbors abundant endophytic bacteria, and some endophytic bacteria showed good potential for the development of microbial fertilizer in the future.

Highly Dispersive Cerium Atoms on Carbon Nanowires as Oxygen Reduction Reaction Electrocatalysts for Zn-Air Batteries.

Highly efficient noble-metal-free electrocatalysts for oxygen reduction reaction (ORR) are essential to reduce the costs of fuel cells and metal-air batteries. Herein, a single-atom Ce-N-C catalyst, constructed of atomically dispersed Ce anchored on N-doped porous carbon nanowires, is proposed to boost the ORR. This catalyst has a high Ce content of 8.55 wt % and a high activity with ORR half-wave potentials of 0.88 V in alkaline media and 0.75 V in acidic electrolytes, which are comparable to widely studied Fe-N-C catalysts. A Zn-air battery based on this material shows excellent performance and durability. Density functional theory calculations reveal that atomically dispersed Ce with adsorbed hydroxyl species (OH) can significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity.

Complete Genome Sequence of the Biocontrol Agent Pseudomonas chlororaphis subsp. aureofaciens SPS-41.

Pseudomonas chlororaphis subsp. aureofaciens SPS-41 is a plant growth-promoting rhizobacterium with biocontrol potential that was isolated from the rhizosphere of sweet potato in Xuzhou, Jiangsu Province, China. Our previous study demonstrated that volatile organic compounds (VOCs) produced by SPS-41 inhibited black spot disease fungi Ceratocystis fimbriata in postharvest sweet potatoes and a variety of other plant pathogens, and the VOCs also displayed strong nematocidal activity. In order to further explore the application potential of this strain, we here report the complete genome sequence of strain SPS-41. The genome consists of one chromosome (6,757,898 bp) with a G+C content 63.10%, which contains 5,951 coding genes, 67 transfer RNA genes, 16 ribosome RNA genes, and 85 other non-coding RNA genes. No plasmid was detected. The information of the genome will provide resources for studying the biocontrol mechanism of this strain.[Formula: see text] Copyright © 2021 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license.

Effective Electrochemical Modulation of SERS Intensity Assisted by Core-Shell Nanoparticles.

An effective and reversible tuning of the intensity of surface-enhanced Raman scattering (SERS) of nonelectroactive molecules at nonresonance conditions by electrochemical means has been developed on plasmonic molecular nanojunctions formed between Au@Ag core-shell nanoparticles (NPs) and a gold nanoelectrode (AuNE) modified with a self-assembled monolayer. The Au@Ag nanoparticle on nanoelectrode (NPoNE) structures are formed in situ by the electrochemical deposition of Ag on AuNPs adsorbed on the AuNE and can be monitored by both the electrochemical current and SERS signals. Instead of introducing molecular changes by the applied electrode potential, the highly effective SERS intensity tuning was achieved by the chemical composition transformation of the ultrathin Ag shell from metallic Ag to insulating AgCl. The electrode potential-induced electromagnetic enhancement (EME) tuning in the Au@Ag NPoNE structure has been confirmed by finite-difference time-domain simulations. Moreover, the specific Raman band associated with Ag-molecule interaction can also be tuned by the electrode potential. Therefore, we demonstrated that the electrode potential could effectively and reversibly modulate both EME and chemical enhancement in Au@Ag NPoNE structures.