Surface Oxygen Defect Engineering of A2B2O7 Pyrochlore Semiconductors Boosts the Electrocatalytic Reduction of CO2-to-HCOOH.

The electrocatalytic conversion of inert CO2 to value-added chemical fuels powered by renewable energy is one of the benchmark approaches to address excessive carbon emissions and achieve carbon-neutral energy restructuring. However, the adsorption/activation of supersymmetric CO2 is facing insurmountable challenges that constrain its industrial-scale applications. Here, this theory-guided study confronts these challenges by leveraging the synergies of bimetallic sites and defect engineering, where pyrochlore-type semiconductor A2B2O7 is employed as research platform and the conversion of CO2-to-HCOOH as the model reaction. Specifically, defect engineering intensified greatly the chemisorption-induced CO2 polarization via the bimetallic coordination, thermodynamically beneficial to the HCOOH production via the *HCO2 intermediate. The optimal V-BSO-430 electrocatalyst with abundant surface oxygen vacancies achieved a superior HCOOH yield of 116.7 mmol h-1 cm-2 at -1.2 VRHE, rivalling the incumbent similar reaction systems. Furthermore, the unique catalytic unit featured with a Bi1-Sn-Bi2 triangular structure, which is reconstructed by defect engineering, and altered the pathway of CO2 adsorption and activation to allow the preferential affinity of the suspended O atom in *HCO2 to H. As a result, V-BSO-430 gave an impressive FEHCOOH of 93% at -1.0 VRHE. This study held promises for inspiring the exploration of bimetallic materials from the massive semiconductor database.

A chiral metal-organic framework/cyclodextrin sensing interface for the chiral discrimination of tryptophan enantiomers.

A chiral metal-organic framework (CMOF) was synthesized by introducing L-histidine (L-His) to zeolitic imidazolate framework-8 (ZIF-8) and then grafting with carboxymethyl-ß-cyclodextrin (CM-ß-CD). Compared with L-His-ZIF-8, the CM-ß-CD-functionalized L-His-ZIF-8 (L-His-ZIF-8-CD) showed significantly enhanced discrimination ability for the tryptophan (Trp) enantiomers owing to the inherent chirality of CM-ß-CD. The specificity of the chiral interface was also studied, and the results indicated that the discrimination ability for Trp enantiomers is significantly stronger than that for the enantiomers of cysteine (Cys) and tyrosine (Tyr), which might be due to the better matching between the indole ring of Trp and the chiral cavity of CM-ß-CD.

Extracellular vesicles derived from cervical cancer cells carrying MCM3AP-AS1 promote angiogenesis and tumor growth in cervical cancer via the miR-93/p21 axis.

Tumor cells can promote angiogenesis by secreting extracellular vesicles (EVs). Meanwhile, tumor-derived EVs can carry long non-coding RNAs to activate pro-angiogenic signaling in endothelial cells. Here, we investigated the role of long non-coding RNA MCM3AP-AS1 carried by cervical cancer (CC) cell-derived EVs in the angiogenesis and the resultant tumor growth in CC, as well as the potential molecular mechanisms. LncRNAs significantly expressed in CC cell-derived EVs and CC were screened, followed by prediction of downstream target genes. EVs were isolated from HcerEpic and CaSki cell supernatants, followed by identification. The expression of MCM3AP-AS1 in CC was analyzed and its interaction with miR-93-p21 was confirmed. Following co-culture system, the role of MCM3AP-AS1 carried by EVs in HUVEC angiogenic ability, CC cell invasion and migration in vitro along with angiogenesis and tumorigenicity in vivo was assayed. MCM3AP-AS1 was overexpressed in CC cell-derived EVs as well as in CC tissues and cell lines. Cervical cancer cell-derived EVs could transfer MCM3AP-AS1 into HUVECs where MCM3AP-AS1 competitively bound to miR-93 and upregulate the expression of the miR-93 target p21 gene. Thus, MCM3AP-AS1 promoted angiogenesis of HUVECs. In the similar manner, MCM3AP-AS1 enhanced CC cell malignant properties. In nude mice, EVs-MCM3AP-AS1 induced angiogenesis and tumor growth. Overall, this study reveals that CC cell-derived EVs may transport MCM3AP-AS1 to promote angiogenesis and tumor growth in CC.

Surface Ru-H Bipyridine Complexes-Grafted TiO2 Nanohybrids for Efficient Photocatalytic CO2 Methanation.

A series of novel surface Ru-H bipyridine complexes-grafted TiO2 nanohybrids were for the first time prepared by a combined procedure of surface organometallic chemistry with post-synthetic ligand exchange for photocatalytic conversion of CO2 to CH4 with H2 as electron and proton donors under visible light irradiation. The selectivity toward CH4 increased to 93.4% by the ligand exchange of 4,4'-dimethyl-2,2'-bipyridine (4,4'-bpy) with the surface cyclopentadienyl (Cp)-RuH complex and the CO2 methanation activity was enhanced by 4.4-fold. An impressive rate of 241.2 µL·g-1·h-1 for CH4 production was achieved over the optimal photocatalyst. The femtosecond transient IR absorption results demonstrated that the hot electrons were fast injected in 0.9 ps from the photoexcited surface 4,4'-bpy-RuH complex into the conduction band of TiO2 nanoparticles to form a charge-separated state with an average lifetime of ca. 50.0 ns responsible for the CO2 methanation. The spectral characterizations indicated clearly that the formation of CO2•- radicals by single electron reduction of CO2 molecules adsorbed on surface oxygen vacancies of TiO2 nanoparticles was the most critical step for the methanation. Such radical intermediates were inserted into the explored Ru-H bond to generate Ru-OOCH species and finally CH4 and H2O in the presence of H2.

Controllable Synthesis of Web-Footed PdCu Nanosheets and Their Electrocatalytic Applications.

Morphological control of noble-metal-based nanocrystals has attracted enormous attention because their catalytic behaviors can be optimized well by adjusting the size and shape. Herein, the controllable synthesis of web-footed PdCu nanosheets via a facile surfactant-free method is reported. It is discovered that the Cu(II) precursor in this synthetic system displays a critical role in growing branches along the lateral of nanosheets. This work demonstrates a Pd-based alloy nanoarchitecture for efficient and stable electrocatalysis of both ethanal and formic acid oxidation reactions.

Prognostic value of circulating tumor cells and its association with the expression of cancer stem cells in nasopharyngeal carcinoma patients.

The release of circulating tumor cells (CTCs) into vasculature is an early event in the metastatic process and the detection of CTCs has been widely used clinically. In addition, cancer stem cells (CSCs) are the source of distant metastasis. However, the relationship between CTCs and CSCs in nasopharyngeal carcinoma (NPC) patients was largely unknown. A total of 93 NPC patients were enrolled in this study. The CTCs in the peripheral blood were detected. The expression of ALDH1A1 in the tumor tissues of the corresponding patients was detected using immunohistochemistry (IHC). The prognostic value of CTCs level and the correlation with the expression of ALDH1A1 was evaluated. Data showed that the detection of CTCs was positively correlated with metastasis (p<0.001). The positive detection of CTCs was also associated with poor overall survival (p=0.025). CTCs ≥2 demonstrated good specificity and sensitivity in predicting distant metastasis, while CTCs ≥8 demonstrated better specificity and sensitivity in predicting prognosis than CTCs ≥2. Furthermore, we found that there was a positive relationship between the detection of CTCs and the expression of ALDH1A1 (p=0.001). The prognosis analysis also demonstrated that high ALDH1A1 expression was correlated with poor overall survival (p=0.006). Our study demonstrated a positive correlation between the CTCs and the expression of CSCs, both were positively correlated with metastasis and poor prognosis. These results indicated that the CTCs might indirectly reflect the expression of CSCs.

Site-Sensitive Selective CO2 Photoreduction to CO over Gold Nanoparticles.

We demonstrate a new case of materials-gene engineering to precisely design photocatalysts with the prescribed properties. Based on theoretical calculations, a phase-doping strategy was proposed to regulate the pathways of CO2 conversion over Au nanoparticles (NPs) loaded TiO2 photocatalysts. As a result, the thermodynamic bottleneck of CO2 -to-CO conversion is successfully unlocked by the incorporation of stable twinning crystal planes into face-centered cubic (fcc) phase Au NPs. Compared to bare pristine TiO2 , the activity results showed that the loading of regular fcc-Au NPs raised the CO production by 18-fold but suppressed the selectivity from 84 % to 75 %, whereas Au NPs with twinning (110) and (100) facets boosted the activity by nearly 40-fold and established near unity CO selectivity. This enhancement is shown to originate from a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy were significantly reduced.

Metal Halide Perovskite Based Heterojunction Photocatalysts.

With fascinating photophysical properties and a strong potential to utilize solar energy, metal halide perovskites (MHPs) have become a prominent feature within photocatalysis research. However, the effectiveness of single MHP photocatalysts is relatively poor. The introduction of a second component to form a heterojunction represents a well-established route to accelerate carrier migration and boost reaction rates, thus increasing the photoactivity. Recently, there have been several scientific advances related to the design of MHP-based heterojunction photocatalysts, including Schottky, type II, and Z-scheme heterojunctions. In this Review, we systematically discuss and critically appraise recent developments in MHP-based heterojunction photocatalysis. In addition, the techniques for identifying the type of active heterojunctions are evaluated and we conclude by briefly outlining the ongoing challenges and future directions for promising photocatalysts based on MHP heterojunctions.

Near-Infrared Light-Driven Photoredox Catalysis by Transition-Metal-Complex Nanodots.

Developing light-harvesting materials with broad spectral response is of fundamental importance in full-spectrum solar energy conversion. We found that, when a series of earth-abundant metal (Cu, Co, Ni and Fe) salts are dissolved in coordinating solvents uniformly dispersed nanodots (NDs) are formed rather than fully dissolving as molecular species. The previously unrecognized formation of this condensed state is ascribed to spontaneous aggregation of molecular transition-metal-complexes (TMCs) via weak intermolecular interactions, which results in redshifted and broadened absorption into the NIR region (200-1100 nm). Typical photoredox reactions, such as carbonylation and oxidative dehydrogenation, well demonstrate the feasibility of efficient utilization of NIR light (λ>780 nm) by TMCs NDs. Our finding provides a conceptually new strategy for extending the absorption towards low energy photons in solar energy harvesting and conversion via photoredox transformations.

Trojans That Flip the Black Phase: Impurity-Driven Stabilization and Spontaneous Strain Suppression in γ-CsPbI3 Perovskite.

The technological progress and widespread adoption of all-organic CsPbI3 perovskite devices is hampered by its thermodynamic instability at room temperature. Because of its inherent tolerance toward deep trap formation, there has been no shortage to exploring which dopants can improve the phase stability. While the relative size of the dopant is important, an assessment of the literature suggests that its relative size and impact on crystal volume do not always reveal what will beneficially shift the phase transition temperature. In this perspective, we analyze the changes in crystal symmetry of CsPbI3 perovskite as it transforms from a thermodynamically stable high-temperature cubic (α) structure into its distorted low-temperature tetragonal (ß) and unstable orthorhombic (γ) perovskite structures. Quantified assessment of the symmetry-adapted strains which are introduced due to changes in temperature and composition show that the stability of γ-CsPbI3 is best rationalized from the point of view of crystal symmetry. In particular, improved thermal-phase stability is directly traced to the suppression of spontaneous strain formation and increased crystal symmetry at room temperature.

The Hole-Tunneling Heterojunction of Hematite-Based Photoanodes Accelerates Photosynthetic Reaction.

Single-atom metal-insulator-semiconductor (SMIS) heterojunctions based on Sn-doped Fe2 O3 nanorods (SF NRs) were designed by combining atomic deposition of an Al2 O3 overlayer with chemical grafting of a RuOx hole-collector for efficient CO2 -to-syngas conversion. The RuOx -Al2 O3 -SF photoanode with a 3.0 nm thick Al2 O3 overlayer gave a >5-fold-enhanced IPCE value of 52.0 % under 370 nm light irradiation at 1.2 V vs. Ag/AgCl, compared to the bare SF NRs. The dielectric field mediated the charge dynamics at the Al2 O3 /SF NRs interface. Accumulation of long-lived holes on the surface of the SF NRs photoabsorber aids fast tunneling transfer of hot holes to single-atom RuOx species, accelerating the O2 -evolving reaction kinetics. The maximal CO-evolution rate of 265.3 mmol g-1 h-1 was achieved by integration of double SIMS-3 photoanodes with a single-atom Ni-doped graphene CO2 -reduction-catalyst cathode; an overall quantum efficiency of 5.7 % was recorded under 450 nm light irradiation.

IL-1ß Promotes Stemness of Tumor Cells by Activating Smad/ID1 Signaling Pathway.

Background: IL-1ß is reported to be involved in cancer development and distant metastasis. However, the underlying mechanism of IL-1ß upon malignant behaviors remains largely unknown. In this study, we aimed to study whether IL-1ß could enhance the stemness traits of tumor cells. Methods: The concentrations of serum IL-1ß in head and neck squamous cell carcinoma (HNSCC) and melanoma patients were detected using ELISA assay. The effect and mechanisms of IL-1ß on tumor cell growth, migration, invasion and stemness characters were studied using HNSCC cell SCC7 and melanoma cell B16-F10. The underlying mechanisms were further explored. Results: Enhanced concentrations of IL-1ß were positively correlated with advanced tumor stage in both HNSCC and melanoma patients. IL-1ß treatment led to a significant increase in tumor growth both in vitro and in vivo. IL-1ß stimulation promoted cell proliferation, colony formation and tumorigenicity. In addition, IL-1ß-stimulated tumor cells gained enhanced capabilities on wounding healing and invasion capabilities. Moreover, IL-1ß stimulation promoted the stem-like capabilities of both HNSCC cells and melanoma cells, including the enrichment of aldehyde dehydrogenase+ (ALDH+) cells, up-regulation of stem cell related markers Nanog, OCT4, and SOX2, sphere formation and chemoresistance. Mechanistically, IL-1ß treatment promoted the phosphorylation of Smad1/5/8 and activated its downstream target inhibitor of differentiation 1 (ID1). Silencing ID1 abrogated sphere formation and upregulated expression of stemness genes which were induced by IL-1ß stimulation. Conclusion: Our data demonstrates that IL-1ß promotes the stemness of HNSCC and melanoma cells through activating Smad/ID1 signal pathway.

CCR9 Promotes Migration and Invasion of Lung Adenocarcinoma Cancer Stem Cells.

Aim: CC chemokine receptor 9 (CCR9) interacts with its exclusive ligand CCL25, resulting in promoting tumor progression and metastasis. However, the effect and mechanisms of CCR9 on lung adenocarcinoma distant metastasis remain largely unknown. To preliminary clarify the underlying mechanisms, we investigate the correlation between CCR9 and ALDH1A1+cancer stem cells (CSCs), as well as the effect of CCR9 on the migration and invasion of CSCs. Methods: Immunohistochemistry was performed to detect the expression of CCR9 in lung adenocarcinoma tissues. The correlations of CCR9 with distant metastasis and overall survival were investigated. Serial paraffin-embedded tissue blocks were used to detect ALDH1A1+CSCs expression. The correlations between CCR9 expression and ALDH1A1+CSCs were evaluated. We further studied the effect of CCR9/CCL25 on the migration and invasion of CSCs using transwell assays. Results: There were positive correlations between CCR9 expression and distant metastasis, as well as poor overall survival. Patients with high CCR9 expression were more likely to develop distant metastasis and demonstrated poorer overall survival than patients with low CCR9 expression. In addition, there was positive correlation between the expression of CCR9 and ALDH1A1 in the same tumor microenvironment. ALDHhigh CSCs demonstrated enhanced expression of CCR9 than ALDHlow cells. Further transwell assays demonstrated that the numbers of CSCs migrated or invaded in response to CCL25 were more than that without CCL25 stimulation. Additional application of anti-CCR9 antibody reversed the CCL25-induced migration and invasion of CSCs. Conclusions: In summary, our study demonstrated that CCR9/CCL25 promoted the migration and invasion of CSCs, which might contribute to distant metastasis and poor overall survival. Our findings provided evidence that CCR9/CCL25 could be used as novel therapeutic targets for lung adenocarcinoma.

N2 Electroreduction to NH3 by Selenium Vacancy-Rich ReSe2 Catalysis at an Abrupt Interface.

Vacancy engineering has been proved repeatedly as an adoptable strategy to boost electrocatalysis, while its poor selectivity restricts the usage in nitrogen reduction reaction (NRR) as overwhelming competition from hydrogen evolution reaction (HER). Revealed by density functional theory calculations, the selenium vacancy in ReSe2 crystal can enhance its electroactivity for both NRR and HER by shifting the d-band from -4.42 to -4.19 eV. To restrict the HER, we report a novel method by burying selenium vacancy-rich ReSe2 @carbonized bacterial cellulose (Vr -ReSe2 @CBC) nanofibers between two CBC layers, leading to boosted Faradaic efficiency of 42.5 % and ammonia yield of 28.3 µg h-1 cm-2 at a potential of -0.25 V on an abrupt interface. As demonstrated by the nitrogen bubble adhesive force, superhydrophilic measurements, and COMSOL Multiphysics simulations, the hydrophobic and porous CBC layers can keep the internal Vr -ReSe2 @CBC nanofibers away from water coverage, leaving more unoccupied active sites for the N2 reduction (especially for the potential determining step of proton-electron coupling and transferring processes as *NN → *NNH).

Hot π-Electron Tunneling of Metal-Insulator-COF Nanostructures for Efficient Hydrogen Production.

A metal-insulator-semiconductor (MIS) photosystem based on covalent organic framework (COF) semiconductors was designed for robust and efficient hydrogen evolution under visible-light irradiation. A maximal H2 evolution rate of 8.42 mmol h-1 g-1 and a turnover frequency of 789.5 h-1 were achieved by using a MIS photosystem prepared by electrostatic self-assembly of polyvinylpyrrolidone (PVP) insulator-capped Pt nanoparticles (NPs) with the hydrophilic imine-linked TP-COFs having =C=O-H-N= hydrogen-bonding groups. The hot π-electrons in the photoexcited n-type TP-COF semiconductors can be efficiently extracted and tunneled to Pt NPs across an ultrathin PVP insulating layer to reduce protons to H2 . Compared to the Schottky-type counterparts, the COF-based MIS photosystems give a 32-fold-enhanced carrier efficiency, attributed to the combined enhancement of photoexcitation rate, charge separation, and oxidation rate of holes accumulated in the valence band of the TP-COF semiconductor.

A Long-Lived Mononuclear Cyclopentadienyl Ruthenium Complex Grafted onto Anatase TiO2 for Efficient CO2 Photoreduction.

This work shows a novel artificial donor-catalyst-acceptor triad photosystem based on a mononuclear C5 H5 -RuH complex oxo-bridged TiO2 hybrid for efficient CO2 photoreduction. An impressive quantum efficiency of 0.56 % for CH4 under visible-light irradiation was achieved over the triad photocatalyst, in which TiO2 and C5 H5 -RuH serve as the electron collector and CO2 -reduction site and the photon-harvester and water-oxidation site, respectively. The fast electron injection from the excited Ru(2+) cation to TiO2 in ca. 0.5 ps and the slow backward charge recombination in half-life of ca. 9.8 µs result in a long-lived D(+) -C-A(-) charge-separated state responsible for the solar-fuel production.

Interim anatase coating layer stabilizes rutile@Crx Oy photoanode for visible-light-driven water oxidation.

Ternary core-shell heterostructured rutile@anatase@Crx Oy nanorod arrays were elaborately designed as photoanodes for efficient photoelectrochemical water splitting under visible-light illumination. The four-fold enhanced and stabilized visible-light photocurrent highlights the unique role of the interim anatase layer in accelerating the interfacial charge transfer from the Crx Oy chromophore to rutile nanorods.

Identification of characteristics and construction of nomogram to predict the survival probability of mesonephric carcinoma patients: A population-based analysis and a case report.

BACKGROUND: Mesonephric carcinoma (MC) is a very rare tumor with less than 70 cases had been reported. The rarity of MC has restricted its research, resulting in the lack of published guidelines. OBJECTIVE: To summarize the characteristics and construct an external-validated nomogram to predict the survival of MC patients. METHOD: Sixty-four qualified patients derived from the Surveillance, Epidemiology, and End Results Plus database, and one patient from the Guangzhou Red Cross Hospital were enrolled. The entire cohort was randomly divided into a development (70%) and a validation cohort (30%). The Kaplan-Meier method and univariate and multivariate Cox regression analyses were applied. Two nomograms were established to predict the 3-to-8-year survival probability of MC patients, which were evaluated by C-index, ROC curves, DCA curves, and calibration plots. RESULTS: The average survival time of MC patients was 84.22 ± 50.66 months. No significant difference was shown among different groups of race, primary site, tumor differentiated grade, and FIGO stages, while different SEER stages did distinguish patients' survival time, which indicated that the SEER stage standards might be a better staging system in the MC patients than FIGO stage (p = .0835). Additional survival analyses showed that MC patients benefited from shorter waiting times to begin treatment, accepting surgery, regional lymph node examination, radiotherapy, and chemotherapy. Two nomograms were established, both of which got satisfied scores in C-index, ROC curves, DCA curves, and calibration plots. CONCLUSION: Sufficient regional lymph nodes examined, and applying radiotherapy in high-risk patients are recommended in MC patients. Nomograms established in the present study had good predicting and discriminating capabilities, which would be helpful in patients' individual risk estimation, management, counseling, and follow-up.

Advancements in Transparent Conductive Oxides for Photoelectrochemical Applications.

Photoelectrochemical cells (PECs) are an important technology for converting solar energy, which has experienced rapid development in recent decades. Transparent conductive oxides (TCOs) are also gaining increasing attention due to their crucial role in PEC reactions. This review comprehensively delves into the significance of TCO materials in PEC devices. Starting from an in-depth analysis of various TCO materials, this review discusses the properties, fabrication techniques, and challenges associated with these TCO materials. Next, we highlight several cost-effective, simple, and environmentally friendly methods, such as element doping, plasma treatment, hot isostatic pressing, and carbon nanotube modification, to enhance the transparency and conductivity of TCO materials. Despite significant progress in the development of TCO materials for PEC applications, we at last point out that the future research should focus on enhancing transparency and conductivity, formulating advanced theories to understand structure-property relationships, and integrating multiple modification strategies to further improve the performance of TCO materials in PEC devices.

Twin boundary defect engineering in Au cocatalyst to promote alcohol splitting for coproduction of H2 and fine chemicals.

The microstructure of Au metal cocatalyst has been shown to significantly influence its optical and electronic properties. However, the impact of Au defect engineering on photocatalytic activity remains underexplored. In this study, we synthesize different Au-TiO2 composites by in-situ hybridizing face-centered cubic (F-Au) and twin boundary defect Au (T-Au) nanoparticles (NPs) onto the surface of TiO2. We find that T-Au NPs with twin defects serve as highly efficient cocatalysts for converting alcohols into their corresponding aldehydes while also generating H2. The optimized T-Au/TiO2 composite yields an H2 evolution rate of 6850 µmol h-1 g-1 and a BAD formation rate of 6830 µmol h-1 g-1, about 38 times higher than that of blank TiO2. Compared to F-Au/TiO2, the T-Au/TiO2 composite enhances charge separation, extends the lifetime of electrons, and provides more active sites for H2 reduction. The twin defect also improves alcohol reactant adsorption, boosting overall photocatalytic performance. This research paves the way for more studies on defect engineering in metal cocatalysts for enhanced catalytic activities in organic synthesis and H2 evolution.