Monitoring Hot Holes in Plasmonic Catalysis on Silver Nanoparticles by Using an Ion Label.

Energetic carriers generated by localized surface plasmon resonance (LSPR) provide an efficient way to drive chemical reactions. However, their dynamics and impact on surface reactions remain unknown due to the challenge in observing hot holes. This makes it difficult to correlate the reduction and oxidation half-reactions involving hot electrons and holes, respectively. Here we detect hot holes in their chemical form, Ag(I), on a Ag surface using surface-enhanced Raman scattering (SERS) of SO32- as a hole-specific label. It allows us to determine the dynamic correlations of hot electrons and holes. We find that the equilibrium of holes is the key factor of the surface chemistry, and the wavelength-dependent plasmonic chemical anode refilling (PCAR) effect plays an important role, in addition to the LSPR, in promoting the electron transfer. This method paves the way for visualizing hot holes with nanoscale spatial resolution toward the rational design of a plasmonic catalytic platform.

Efficient C(sp3)-H Bond Oxidation on Perovskite Quantum Dots Based on Ce-Oxygen Affinity.

Perovskite quantum dots (QDs) have shown attractive prospects in the field of visible photocatalysis, especially in the synthesis of high value-added chemicals. However, under aerobic conditions, the stable operation of QD catalysts has been limited by the reactive oxygen species (ROS) generated by photoexcitation, especially superoxide species O2⋅-. Here, we propose a strategy of Ce3+ doping in perovskite QDs to guide superoxide species for photocatalytic oxidation reactions. In C(sp3)-H bond oxidation of hydrocarbons, superoxide species were rapidly generated and efficiently utilized on the surface of perovskite QDs, which achieves the stable operation of the catalytic system and obtains a high product conversion rate (15.3 mmol/g/h for benzaldehydes). The mechanism studies show that the strong Ce-oxygen affinity accelerates the relaxation process of photoinduced exciton transfer to superoxide species and inhibits the radiative recombination pathway. This work provides a new idea of utilizing oxygen species on perovskite surface and broadens the design strategy of high-performance QD photocatalysts.

Interfacial Evolution on Co-based Oxygen Evolution Reaction Electrocatalysts Probed by Using In Situ Surface-Enhanced Raman Spectroscopy.

Disclosing the roles of reactive sites at catalytic interfaces is of paramount importance for understanding the reaction mechanism. However, due to the difficulties in the detection of reaction intermediates in the complex heterophase reaction system, disentangling the highly convolved roles of different surface atoms remains challenging. Herein, we used CoOx as a model catalyst to study the synergy of CoTd2+ and CoOh3+ active sites in the electrocatalytic oxygen evolution reaction (OER). The formation and evolution of reaction intermediates on the catalyst surface during the OER process were investigated by in situ surface-enhanced Raman spectroscopy (SERS). According to the SERS results in ion-substitution experiments, CoOh3+ is the catalytic site for the conversion of OH- to O-O- intermediate species (1140-1180 cm-1). CoOOH (503 cm-1) and CoO2 (560 cm-1) active centers generated during the OER, at the original CoTd2+ sites of CoOx, eventually serve as the O2 release sites (conversion of O-O- intermediate to O2). The mechanism was further confirmed on Co2+-Co3+ layered double hydroxides (LDHs), where an optimal ratio of 1:1.2 (Co2+/Co3+) is required to balance O-O- generation and O2 release. This work highlights the synergistic role of metal atoms at different valence statuses in water oxidation and sheds light on surface component engineering for the rational design of high-performance heterogeneous catalysts.

In Situ Monitoring of Palladium-Catalyzed Chemical Reactions by Nanogap-Enhanced Raman Scattering using Single Pd Cube Dimers.

The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneously catalyzed reactions is the need of plasmonically active nanostructures for signal enhancement. Here, we show that the assembly of catalytically active transition-metal nanoparticles into dimers boosts their intrinsically insufficient plasmonic activity at the monomer level by several orders of magnitude, thereby enabling the in situ SERS monitoring of various important heterogeneously catalyzed reactions at the single-dimer level. Specifically, we demonstrate that Pd nanocubes (NCs), which alone are not sufficiently plasmonically active as monomers, can act as a monometallic yet bifunctional platform with both catalytic and satisfactory plasmonic activity via controlled assembly into single dimers with an ∼1 nm gap. Computer simulations reveal that the highest enhancement factors (EFs) occur at the corners of the gap, which has important implications for the SERS-based detection of catalytic conversions: it is sufficient for molecules to come in contact with the "hot spot corners", and it is not required that they diffuse deeply into the gap. For the widely employed Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, we demonstrate that such Pd NC dimers can be employed for in situ kinetic SERS monitoring, using a whole series of aryl halides as educts. Our generic approach based on the controlled assembly into dimers can easily be extended to other transition-metal nanostructures.

Several Key Factors for Efficient Electrocatalytic Water Splitting: Active Site Coordination Environment, Morphology Changes and Intermediates Identification.

Water-splitting has emerged as a promising alternative strategy to produce clean hydrogen fuel. However, current electrocatalytic water splitting suffers from sluggish kinetics, thus developing efficient electrocatalysts is crucial. Identifying reaction centers discloses the reaction mechanism and will undoubtedly facilitate the design and optimization of efficient water splitting electrocatalysts. This review summarizes several advances involving the identification of the actual active sites and intermediates capture on the catalytic surface. The morphology and valence states change on 2D materials are chose to illustrate how structural evolution affect catalytic activity. Specifically, in situ/ex situ electron microscopy techniques that used for the characterization of catalytic sites, and spectroscopy techniques that used to detect active intermediates at the molecular level are highlighted. In addition, several perspectives, such as the development of new in situ techniques and electrokinetic analysis methods, are emphasized to shed light on future research.

Surface-Enhanced Raman Spectroscopic Evidence of Key Intermediate Species and Role of NiFe Dual-Catalytic Center in Water Oxidation.

NiFe-based electrocatalysts have attracted great interests due to the low price and high activity in oxygen evolution reaction (OER). However, the complex reaction mechanism of NiFe-catalyzed OER has not been fully explored yet. Detection of intermediate species can bridge the gap between OER performances and catalyst component/structure properties. Here, we performed label-free surface-enhanced Raman spectroscopic (SERS) monitoring of interfacial OER process on Ni3 FeOx nanoparticles (NPs) in alkaline medium. By using bifunctional Au@Ni3 FeOx core-satellite superstructures as Raman signal enhancer, we found direct spectroscopic evidence of intermediate O-O- species. According to the SERS results, Fe atoms are the catalytic sites for the initial OH- to O-O- oxidation. The O-O- species adsorbed across neighboring Fe and Ni sites experiences further oxidation caused by electron transfer to NiIII and eventually forms O2 product.

Ag2 S-CdS p-n Nanojunction-Enhanced Photocatalytic Oxidation of Alcohols to Aldehydes.

Selective oxidation of alcohols to aldehydes under mild conditions is important for the synthesis of high-value-added organic intermediates but still very challenging. For most of the thermal and photocatalytic systems, noble metal catalysts or harsh reaction conditions are required. Herein, the synthesis and use of Ag2 S-CdS p-n nanojunctions as an efficient photocatalyst for selective oxidation of a series of aromatic alcohols to their corresponding aldehydes is reported. High quantum efficiencies (59.6% and 36.9% under 380 and 420 nm, respectively) are achieved in air atmosphere at room temperature. Photoluminescence and photo-electrochemical tests show that the excellent performance is mainly due to the p-n junction-enhanced charge separation and transfer for the activation of both O2 (in air) and substrates. This study demonstrates the potential of p-n junction in photocatalytic synthesis under mild conditions.

Synthesis of a Gold-Metal Oxide Core-Satellite Nanostructure for In†Situ SERS Study of CuO-Catalyzed Photooxidation.

This work reports on an assembling-calcining method for preparing gold-metal oxide core-satellite nanostructures, which enable surface-enhanced Raman spectroscopic detection of chemical reactions on metal oxide nanoparticles. By using the nanostructure, we study the photooxidation of Si-H catalyzed by CuO nanoparticles. As evidenced by the in situ spectroscopic results, oxygen vacancies of CuO are found to be very active sites for oxygen activation, and hydroxide radicals (*OH) adsorbed at the catalytic sites are likely to be the reactive intermediates that trigger the conversion from silanes into the corresponding silanols. According to our finding, oxygen vacancy-rich CuO catalysts are confirmed to be of both high activity and selectivity in photooxidation of various silanes.

C-H Arylation on Nickel Nanoparticles Monitored by In†Situ Surface-Enhanced Raman Spectroscopy.

Bifunctional Au@Ni core-satellite nanostructures synthesized by a one-step assembly method were employed for in situ surface-enhanced Raman spectroscopic (SERS) monitoring of Ni-catalyzed C-C bond-forming reactions. Surprisingly, the reaction that was thought to be an Ullmann-type self-coupling reaction, was found to be a cross-coupling reaction proceeding by photoinduced aromatic C-H bond arylation. In situ SERS monitoring enabled the discovery, and a series of biphenyl compounds were synthesized photocatalytically, and at room temperature, using cheap Ni nanoparticle catalysts.

Cadmium Exposure-Sedum alfredii Planting Interactions Shape the Bacterial Community in the Hyperaccumulator Plant Rhizosphere.

Rhizospheric bacteria play important roles in plant tolerance and activation of heavy metals. Understanding the bacterial rhizobiome of hyperaccumulators may contribute to the development of optimized phytoextraction for metal-polluted soils. We used 16S rRNA gene amplicon sequencing to investigate the rhizospheric bacterial communities of the cadmium (Cd) hyperaccumulating ecotype (HE) Sedum alfredii in comparison to its nonhyperaccumulating ecotype (NHE). Both planting of two ecotypes of S. alfredii and elevated Cd levels significantly decreased bacterial alpha-diversity and altered bacterial community structure in soils. The HE rhizosphere harbored a unique bacterial community differing from those in its bulk soil and NHE counterparts. Several key taxa from Actinobacteria, Bacteroidetes, and TM7 were especially abundant in HE rhizospheres under high Cd stress. The actinobacterial genus Streptomyces was responsible for the majority of the divergence of bacterial community composition between the HE rhizosphere and other soil samples. In the HE rhizosphere, the abundance of Streptomyces was 3.31- to 16.45-fold higher than that in other samples under high Cd stress. These results suggested that both the presence of the hyperaccumulator S. alfredii and Cd exposure select for a specialized rhizosphere bacterial community during phytoextraction of Cd-contaminated soils and that key taxa, such as the species affiliated with the genus Streptomyces, may play an important role in metal hyperaccumulation.IMPORTANCESedum alfredii is a well-known Cd hyperaccumulator native to China. Its potential for extracting Cd relies not only on its powerful uptake, translocation, and tolerance for Cd but also on processes underground (especially rhizosphere microbes) that facilitate root uptake and tolerance of the metal. In this study, a high-throughput sequencing approach was applied to gain insight into the soil-plant-microbe interactions that may influence Cd accumulation in the hyperaccumulator S. alfredii Here, we report the investigation of rhizosphere bacterial communities of S. alfredii in phytoremediation of different levels of Cd contamination in soils. Moreover, some key taxa in its rhizosphere identified in the study, such as the species affiliated with genus Streptomyces, may shed new light on the involvement of bacteria in phytoextraction of contaminated soils and provide new materials for phytoremediation optimization.

[Associations between hepatitis B virus x gene mutations and hepatocellular carcinoma].

OBJECTIVE: To investigate the association of mutations in the hepatitis B virus (HBV) X gene (HBX, encoding the HBx protein) and development of hepatocellular carcinoma (HCC). METHODS: Forty-four patients with HBV-related HCC participated in the study, along with 76 patients with chronic HBV infection who assessed as controls. All patients had serum HBV DNA levels that were higher than 10(3) copies/ml. Extracted HBV DNA was subjected to nested PCR to amplify the HBX gene, followed by direct sequencing. All sequencing data were compared to the consensus HBV sequence to identify mutations. The sequencing data were analyzed by Chromas and SeqMan software. RESULTS: Mutations of G1467C, G/C1479A, C1485T and C1653T in the X region were found, but did not show any significant difference in occurrence between the HCC group and the chronic HBV infection group (P>0.05). The T1674C mutation in the X region, however, occurred more frequently in the HCC group (29.27% vs.6.67%, P<0.05). Prevalence of the T1753C mutation and the A1762T/G1764A double mutation in the BCP region was significantly higher in the HCC group than in the chronic HBV infection group (P<0.05) and in the group of patients with hepatitis B e antigen (HBeAg)-negative status compared to the patients with HBeAg-positive status (P<0.05). CONCLUSION: Incidence of the T1674C mutation in the X region and of the T1753C mutation and the A1762T/G1764A double mutation in the BCP region was higher for patients with HBV-related HCC; the T1753C mutation and the A1762T/G1764A double mutation may inhibit the formation of HBeAg.

A multi-functional nano-platform based on LiGa4.99O8:Cr0.01/IrO2 with near infrared-persistent luminescence, "afterglow" photodynamic and photo-thermal functions.

Multi-functionalised nano-platforms based on persistent-luminescence nanoparticles (PLNPs) have attracted considerable attention for biomedical applications owing to their lack of background noise and suitability for in vivo imaging without the need for in situ excitation. However, nano-platforms based on PLNPs for continuous photodynamic therapy (PDT) are currently lacking. Herein, we report a nano-platform (LiGa4.99O8:Cr0.01/IrO2, LGO:Cr/IrO2) prepared using PLNPs (LiGa4.99O8:Cr0.01, LGO:Cr) covalently bonded with iridium oxide nanoparticles (IrO2 NPs), producing near-infrared (NIR) persistent luminescence, "afterglow" PDT and photo-thermal therapy (PTT) effects. The LGO:Cr/IrO2 not only exhibits NIR-persistent luminescence at 719 nm and a PTT effect under 808 nm irradiation but also a continuous "afterglow" PDT effect without the need for in situ excitation owing to persistent energy transfer from LGO:Cr to the IrO2 NPs, in turn generating reactive oxygen species (ROS). This multi-functional nano-platform is expected to further promote the application of PLNPs in tumour treatment.

Long-lived carriers-promoted photocatalytic deuteration of halides with D2O as the deuterium source over Cu doped quantum dots.

Deuterium labeling is a highly valuable yet challenging subject of research in various scientific fields. Conventional deuteration methods often involve harsh reaction conditions and suffer from limited reactivity and selectivity. Herein, we report a visible light-driven C-X (X = halogen) to C-D (D = deuterium) exchange strategy over copper-doped cadmium sulfide quantum dots (Cu-CdS QDs) under mild conditions, eliminating the need for noble metal catalysts and expensive deuterium sources. The conversion of aryl halides into deuterated products using Cu-CdS QDs reaches up to 99%, which is four times higher than that achieved using pristine CdS QDs. The substantial enhancement in the photocatalytic activity of the QDs can be primarily attributed to the generation of long-lived charge carriers (approximately 6 µs) induced by Cu doping. Mechanistic studies reveal that the Cu dopants considerably retard the recombination of photoinduced carriers by creating intermediate energy levels that serve as hole trapping centers in CdS QDs, thereby improving the electron utilization efficiency in energetically demanding photoreduction reactions. Additionally, the introduction of Cu increases the energy offset between the conduction band of CdS QDs and molecular acceptors, facilitating the electron transfer process. Upon visible light irradiation, a series of aryl halides can be efficiently converted into the desired deuterated compounds using D2O as the deuterium source. This work demonstrates that regulating charge carrier dynamics in ultrasmall QD-based photocatalysts is a promising strategy for promoting organic transformations.

Insight from the association between critical thinking and English argumentative writing: catering to English learners' writing ability.

Introduction: English argumentative writing (EAW) is a 'problem-solving' cognitive process, and its relationship with critical thinking has drawn attention in China. This is because fostering EAW proficiency is a crucial element but a challenging task for Chinese high school English teaching and learning. The present study examined how critical thinking is related to Chinese high school students' EAW performance. The study identified eight critical thinking disposition (CTD) subscales and aims to determine whether EAW and CTD are correlated. Methods: A questionnaire modified from the Chinese Version Critical Thinking Disposition Inventory (CTDI-CV) and the Evaluation Criteria for English Argumentative Writing (ECEAW) were employed in this study. Both instruments were administered to 156 students from Grade 12. A purposive sampling of high school students was used in this study. Student EAW performance was scored by two experts based on the Evaluation Criteria for English Argumentative Writing. Results: A significant relationship was found between students' CTD and EAW abilities. Furthermore, among the eight CTD subdispositions, cognitive maturity, truth-seeking, analyticity, and justice were found to be positively correlated with EAW, and they all were found to be the main predictors of EAW proficiency among high school students. Conclusion: Zhangzhou high school students' CTDs were overall positive, and students' EAW performance correlated significantly with the overall CTD and its four subdispositions of cognitive maturity, truth-seeking, analyticity, and justice. These four subdispositions showed a significantly predictive validity on EAW performance as well.

Light inhibition of hydrogenation reactions on Au-Pd nanocoronals as plasmonic switcher in catalysis.

Light, as a powerful energy source, has motivated the many endeavors of chemists in photochemical transformations. We were delighted to find that light has an inhibition effect on hydrogenation reactions. Exploring this previously unperceived effect will bring renewed understanding of interactions of light and matter. This work provides a breakthrough in ways to remotely control chemical reactions by light.

Hollow Hierarchical Cu2 O-Derived Electrocatalysts Steering CO2 Reduction to Multi-Carbon Chemicals at Low Overpotentials.

The electrochemical reduction of carbon dioxide into multi-carbon products (C2+ ) using renewably generated electricity provides a promising pathway for energy and environmental sustainability. Various oxide-derived copper (OD-Cu) catalysts have been showcased, but still require high overpotential to drive C2+ production owing to sluggish carbon-carbon bond formation and low CO intermediate (*CO) coverage. Here, the dilemma is circumvented by elaborately devising the OD-Cu morphology. First, computational studies propose a hollow and hierarchical OD-Cu microstructure that can generate a core-shell microenvironment to inhibit CO evolution and accelerate *CO dimerization via intermediate confinement and electric field enhancement, thereby boosting C2+ generation. Experimentally, the designed nanoarchitectures are synthesized through a heteroseed-induced approach followed by electrochemical activation. In situ spectroscopic studies further elaborate correlation between *CO dimerization and designed architectures. Remarkably, the hierarchical OD-Cu manifests morphology-dependent selectivity of CO2 reduction, giving a C2+ Faradaic efficiency of 75.6% at a considerably positive potential of -0.55 V versus reversible hydrogen electrode.

Nanopatterning of Si(001) for bottom-up fabrication of nanostructures.

The epitaxial growth of Si on Si(001) under conditions at which the (2 × n) superstructure is forming has been investigated by scanning tunneling microscopy and Monte Carlo simulations. Our experiments reveal a periodic change of the surface morphology with the surface coverage of Si. A regular (2 × n) stripe pattern is observed at coverages of 0.7-0.9 monolayers that periodically alternates with less dense surface structures at lower Si surface coverages. The MC simulations show that the growth of Si is affected by step-edge barriers, which favors the formation of a rather uniform two-dimensional framework-like configuration. Subsequent deposition of Ge onto the (2 × n) stripe pattern yields a dense array of small Ge nanostructures.

Exploration of the Immunotyping Landscape and Immune Infiltration-Related Prognostic Markers in Ovarian Cancer Patients.

Background: Increasing evidence indicates that immune cell infiltration (ICI) affects the prognosis of multiple cancers. This study aims to explore the immunotypes and ICI-related biomarkers in ovarian cancer. Methods: The ICI levels were quantified with the CIBERSORT and ESTIMATE algorithms. The unsupervised consensus clustering method determined immunotypes based on the ICI profiles. Characteristic genes were identified with the Boruta algorithm. Then, the ICI score, a novel prognostic marker, was generated with the principal component analysis of the characteristic genes. The relationships between the ICI scores and clinical features were revealed. Further, an ICI signature was integrated after the univariate Cox, lasso, and stepwise regression analyses. The accuracy and robustness of the model were tested by three independent cohorts. The roles of the model in the immunophenoscores (IPS), tumor immune dysfunction and exclusion (TIDE) scores, and immunotherapy responses were also explored. Finally, risk genes (GBP1P1, TGFBI, PLA2G2D) and immune cell marker genes (CD11B, NOS2, CD206, CD8A) were tested by qRT-PCR in clinical tissues. Results: Three immunotypes were identified, and ICI scores were generated based on the 75 characteristic genes. CD8 TCR pathways, chemokine-related pathways, and lymphocyte activation were critical to immunophenotyping. Higher ICI scores contributed to better prognoses. An independent prognostic factor, a three-gene signature, was integrated to calculate patients' risk scores. Higher TIDE scores, lower ICI scores, lower IPS, lower immunotherapy responses, and worse prognoses were revealed in high-risk patients. Macrophage polarization and CD8 T cell infiltration were indicated to play potentially important roles in the development of ovarian cancer in the clinical validation cohort. Conclusions: Our study characterized the immunotyping landscape and provided novel immune infiltration-related prognostic markers in ovarian cancer.

Quantifying Hot Electron Energy Contributions in Plasmonic Photocatalysis Using Electrochemical Surface-Enhanced Raman Spectroscopy.

Due to the challenge in measuring hot electron energy under reaction conditions, very few studies focus on experimental determination of hot carrier energy. Here, we adjust the energy state of free electrons in Au nanoparticles to quantify the hot electron energy in plasmonic photocatalysis. Reactant molecules with different reduction potentials such as 4-nitrothiophenol (4-NTP), 4-iodothiophenol (4-ITP), etc. are chosen as molecular probes to investigate the reducing ability of hot electrons. By comparing the voltage required to achieve the same conversion of photo- and electro-reaction pathways, we calibrate the maximum energy efficiency of hot electrons in 4-NTP reduction to be 0.32 eV, which is much lower than the excitation photon energy of 1.96 eV. Our work provides insight into the energy distribution of hot electrons and will be helpful for rational design of highly efficient plasmon-mediated chemical reactions.

Universal linker-free assembly of core-satellite hetero-superstructures.

Colloidal superstructures comprising hetero-building blocks often show unanticipated physical and chemical properties. Here, we present a universal assembly methodology to prepare hetero-superstructures. This straightforward methodology allows the assembly of building block materials varying from inorganic nanoparticles to living cells to form superstructures. No molecular linker is required to bind the building blocks together and thus the products do not contain any unwanted adscititious material. The Fourier transform infrared spectra, high resolution transmission electron microscopic images and nanoparticle adhesion force measurement results reveal that the key to self-organization is stripping surface ligands by adding non-polar solvents or neutralizing surface charge by adding salts, which allow us to tune the balance between van der Waals attraction and electrostatic repulsion in the colloid so as to trigger the assembling process. As a proof-of-concept, the superior photocatalytic activity and single-particle surface-enhanced Raman scattering of the corresponding superstructures are demonstrated. Our methodology greatly extends the scope of building blocks for superstructure assembly and enables scalable construction of colloidal multifunctional materials.