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.

Ensemble Extreme Learning Machine Method for Hemoglobin Estimation Based on PhotoPlethysmoGraphic Signals.

Non-invasive detection of hemoglobin (Hb) concentration is of great clinical value for health screening and intraoperative blood transfusion. However, the accuracy and stability of non-invasive detection still need to be improved to meet clinical requirement. This paper proposes a non-invasive Hb detection method using ensemble extreme learning machine (EELM) regression based on eight-wavelength PhotoPlethysmoGraphic (PPG) signals. Firstly, a mathematical model for non-invasive Hb detection based on the Beer-Lambert law is established. Secondly, the captured eight-channel PPG signals are denoised and fifty-six feature values are extracted according to the derived mathematical model. Thirdly, a recursive feature elimination (RFE) algorithm is used to select the features that contribute most to the Hb prediction. Finally, a regression model is built by integrating several independent ELM models to improve prediction stability and accuracy. Experiments conducted on 249 clinical data points (199 cases as the training dataset and 50 cases as the test dataset) evaluate the proposed method, achieving a root mean square error (RMSE) of 1.72 g/dL and a Pearson correlation coefficient (PCC) of 0.76 (p < 0.01) between predicted and reference values. The results demonstrate that the proposed non-invasive Hb detection method exhibits a strong correlation with traditional invasive methods, suggesting its potential for non-invasive detection of Hb concentration.

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.

Remarkably Enhanced Luminol/H2O2 Chemiluminescence with Excellent Peroxidase-like Activity of FeCoNi-based Metal-Organic Xerogels for the Sensitive Detection of Dopamine.

Metal-organic gels (MOGs) are a category of metal-organic smart soft materials with large specific surface areas, loose porous structures, and open metal active sites. In this work, trimetallic Fe(III)Co(II)Ni(II)-based MOGs (FeCoNi-MOGs) were synthesized at room temperature via a simple and mild one-step procedure. Fe3+, Co2+, and Ni2+ were the three central metal ions in it, while 1,3,5-benzenetricarboxylic acid (H3BTC) served as the ligand. The solvent enclosed in it was then removed by freeze-drying to get the corresponding metal-organic xerogels (MOXs). The as-prepared FeCoNi-MOXs have excellent peroxidase-like activity and can significantly enhance luminol/H2O2 chemiluminescence (CL) by more than 3000 times, which is very effective compared with other reported MOXs. Based on the inhibitory effect of dopamine on the CL of the FeCoNi-MOXs/luminol/H2O2 system, a simple, rapid, sensitive, and selective CL method for dopamine detection was established with a linear range of 5-1000 nM and a limit of detection of 2.9 nM (LOD, S/N = 3). Furthermore, it has been effectively used for the quantitative measurement of dopamine in dopamine injections and human serum samples, with a recovery rate of 99.5-109.1%. This research brings up prospects for the application of MOXs with peroxidase-like activity in CL.

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.

Whole exome sequencing identifies a novel homozygous missense mutation of LHCGR gene in primary infertile women with empty follicle syndrome.

AIM: The genetic basis of empty follicle syndrome (EFS) is largely unknown, and the aim of this study was to investigate the genetic causes of EFS in primary infertile women. METHODS: Four affected women diagnosed with anovulation were recruited, and whole exome sequencing (WES) was requested for the genetic diagnosis of the cases. One hundred healthy controls were verified by Sanger sequencing. RESULTS: A novel homozygous variant of the LHCGR gene (NM_000233:c.1847C>A) was revealed in one affected individual by WES. Trios analysis of the mutation revealed an autosomal recessive pattern. This LHCGR variant was absent in 100 healthy controls and predicted to be highly damaging to the function of LHCGR. CONCLUSIONS: The novel variant extends the mutational spectrum of the LHCGR gene associated with female sterility, which promotes the prognostic value of testing for LHCGR mutations in infertile women with EFS.

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.

Manipulating the Injected Energy Flux via Host-Sensitized Nanostructure for Improving Multiphoton Upconversion Luminescence of Tm3.

Combating the concentration quenching effect by increasing the concentration of sensitized rare-earth ions in rational design upconversion nanostructure will make it easier to utilize injection energy flux and transfer it to emitters, resulting in improved upconversion luminescence (UCL). We proposed a host-sensitized nanostructure (active core@luminescent shell@inert shell) to improve multiphoton UCL of Tm3+ based on the LiLnF4 host. Yb3+ ions were isolated in the core as energy absorbents, and Tm3+ was doped in the interior LiYbF4 host shell. Compared with sandwich structured nanocrystals (Y@Y:Yb/Tm@Y), reverse structure (YbTm@Yb@Y), and fully doped structure (YbTm@YbTm@Y), the proposed structure achieved the highest efficiency of multiphoton UCL and favored a better FRET-based application performance as the Tm3+ located at an optimized spatial distribution. Furthermore, steady-state and dynamic analysis results demonstrate that by manipulating the spatial distribution of the active ions, excited energy can be tuned to enable multiphoton upconversion enhancement, overcoming the conventional limitations.

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.

Quantitative Proteomic Analysis Reveals the Key Molecular Events Driving Phaeocystis globosa Bloom and Dissipation.

Phaeocystis globosa is a marine-bloom-forming haptophyte with a polymorphic life cycle alternating between free-living cells and a colonial morphotype, that produces high biomass and impacts ecological structure and function. The mechanisms of P. globosa bloom formation have been extensively studied, and various environmental factors are believed to trigger these events. However, little is known about the intrinsic biological processes that drive the bloom process, and the mechanisms underlying P. globosa bloom formation remain enigmatic. Here, we investigated a P. globosa bloom occurring along the Chinese coast and compared the proteomes of in situ P. globosa colonies from bloom and dissipation phases using a tandem mass tag (TMT)-based quantitative proteomic approach. Among the 5540 proteins identified, 191 and 109 proteins displayed higher abundances in the bloom and dissipation phases, respectively. The levels of proteins involved in photosynthesis, pigment metabolism, nitrogen metabolism, and matrix substrate biosynthesis were distinctly different between these two phases. Ambient nitrate is a key trigger of P. globosa bloom formation, while the enhanced light harvest and multiple inorganic carbon-concentrating mechanisms support the prosperousness of colonies in the bloom phase. Additionally, colonies in the bloom phase have greater carbon fixation potential, with more carbon and energy being fixed and flowing toward the colonial matrix biosynthesis. Our study revealed the key biological processes underlying P. globosa blooms and provides new insights into the mechanisms behind bloom formation.

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.

Clinical exome sequencing identifies novel compound heterozygous mutations of the WEE2 gene in primary infertile women with fertilization failure.

OBJECTIVE: The genetic basis of fertilization failure after intracytoplasmic sperm injection (ICSI) is largely unknown and the aim of this study is to investigate the genetic causes of fertilization failure in primary infertile women. METHODS: Six affected women diagnosed with infertility and fertilization failure were recruited. The genetically pathogenic factor of their fertilization failures were investigated by clinical exome sequencing. One hundred healthy controls were verified by Sanger sequencing. RESULTS: Novel compound heterozygous mutations c.625G > T and c.759-2A > G of WEE2 in one affected individual were revealed by clinical exome sequencing. Trios analysis of the mutations represented an autosomal recessive pattern. The nonsense mutation c.625G > T (p.Glu209*) indicated the truncation of the WEE2 protein and c.759-2A > G was predicted to affect the splicing. CONCLUSIONS: The novel variants extend the spectrum of WEE2 mutations, which promotes the prognostic value of testing for WEE2 mutations in infertile women with fertilization failure.

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.

Does Temporal Expectation Driven by Rhythmic Cues Differ From That Driven by Symbolic Cues Across the Millisecond and Second Range?

Temporal expectation relies on different predictive information, such as regular rhythms and symbolic cues, to direct attention to a future moment in time to optimize behaviour. However, whether differences exist between temporal expectations driven by regular rhythms and symbolic cues has not been clearly established. In this study, 20 participants performed two temporal expectation tasks in which a rhythmic cue or a symbolic cue indicated (70% expected) that the target would appear after an interval of 500 ms (short), 1,500 ms (medium), or 2,500 ms (long). We found larger cueing effects for the rhythmic cued task than for the symbolic cued task during the short interval, indicating that rhythmic cues were more effective in improving performance. Furthermore, no significant difference was found during the longer interval, reflect that the behavioural differences between the two forms of temporal expectations were likely to diminish as the time interval increased. Thus, we speculate that the temporal expectation driven by rhythmic cues differs from that driven by symbolic cues only in the limited time range; however, the mechanisms underlying the two forms of temporal expectations trend to become more similar over increasing temporal scales.

3D Printed Rotating Acentric Binary-Disk Electrode.

Rotating ring-disk electrode (RRDE) is a generator-collector electrochemical system widely used as an electroanalytical and kinetic device. However, RRDEs are costly and difficult to fabricate, particularly when the electrode material is fragile, small, and scarce. Taking advantage of readily available 3D printing technology an alternative generator-collector system was developed: rotating acentric binary-disk electrode (RABDE). RABDE consists of two close acentric disk electrodes arranged in a cylindrical matrix so that the line connecting their centers is perpendicular to radius of the device passing through the center of generator electrode. In contrast to RRDE that is based on radial flow velocity for mass transfer between the generator and the collector, RABDE mostly takes advantage of the larger tangential flow velocity. RABDE thus exhibits higher current densities than RRDE for a same rotation rate and evidences much better electroanalytical performances. These increased performances were tested and quantified using typical analytes: potassium ferricyanide system, copper ion system, and oxygen reduction reaction in alkaline solution.

Sensitive electrochemical detection of sodium azide based on the electrocatalytic activity of the pasting liquid of a carbon paste electrode.

Sodium azide (NaN3) is highly toxic and widely used in, for example, automobile airbags and biochemical laboratories. The electrochemical detection of sodium azide on commonly used electrodes is challenging due to sluggish electron transfer, but it has been achieved using a boron-doped diamond thin-film electrode and a highly oriented pyrolytic graphite electrode. Utilizing the electrocatalytic activity of the pasting liquid of a carbon paste electrode, we developed an effective method for the electrochemical detection of sodium azide in which silicone oil was employed as the pasting liquid of the carbon paste electrode. This simple and cheap silicone-oil-based carbon paste electrode exhibited comparable sensitivity to the boron-doped diamond thin-film electrode and highly oriented pyrolytic graphite electrode. The limit of detection for sodium azide at the silicone-oil-based carbon paste electrode was found to be 0.1 µM. Recoveries from diluted human serum samples were between 97.2 and 101.3%. Graphical abstract ᅟ.

Mutation analysis of the TUBB8 gene in primary infertile women with arrest in oocyte maturation.

Tubulin beta eight class VIII (TUBB8) is a subtype of ß-tubulin that only exists in primates. Mutations in the TUBB8 gene have been proven to cause oocyte maturation arrest. The aim of this study was to identify the new types of mutations in TUBB8. Six women (families) with oocyte maturation arrest and 100 healthy controls were recruited. The sequence of the TUBB8 gene was amplified and analyzed by Sanger sequencing, which revealed a de novo heterozygous variant c.292G > A (p.G98R) of TUBB8 in one affected individual. This TUBB8 variant was absent in the 100 fertile females and was predicted to be highly damaging to the function of the TUBB8 protein by SIFT and PolyPhen-2. This novel variant extends the spectrum of TUBB8 mutations and the presence of a TUBB8 mutation is being considered to be indicative of a poor prognosis for the success of assisted reproductive treatment.