Ornithine δ-aminotransferase OsOAT is critical for male fertility and cold tolerance during rice plant development.

Cold stress is a major factor limiting the production and geographical distribution of rice (Oryza sativa) varieties. However, the molecular mechanisms underlying cold tolerance remain to be elucidated. Here, we report that ornithine δ-aminotransferase (OsOAT) contributes to cold tolerance during the vegetative and reproductive development of rice. osoat mutant was identified as a temperature-sensitive male sterile mutant with deformed floral organs and seedlings sensitive to cold stress. Comparative transcriptome analysis showed that OsOAT mutation and cold treatment of the wild-type plant led to similar changes in the global gene expression profiles in anthers. OsOAT genes in indica rice Huanghuazhan (HHZ) and japonica rice Wuyungeng (WYG) are different in gene structure and response to cold. OsOAT is cold-inducible in WYG but cold-irresponsive in HHZ. Further studies showed that indica varieties carry both WYG-type and HHZ-type OsOAT, whereas japonica varieties mostly carry WYG-type OsOAT. Cultivars carrying HHZ-type OsOAT are mainly distributed in low-latitude regions, whereas varieties carrying WYG-type OsOAT are distributed in both low- and high-latitude regions. Moreover, indica varieties carrying WYG-type OsOAT generally have higher seed-setting rates than those carrying HHZ-type OsOAT under cold stress at reproductive stage, highlighting the favorable selection for WYG-type OsOAT during domestication and breeding to cope with low temperatures.

A Dual-Modal, Label-Free Raman Imaging Method for Rapid Virtual Staining of Large-Area Breast Cancer Tissue Sections.

As one of the most common cancers, accurate, rapid, and simple histopathological diagnosis is very important for breast cancer. Raman imaging is a powerful technique for label-free analysis of tissue composition and histopathology, but it suffers from slow speed when applied to large-area tissue sections. In this study, we propose a dual-modal Raman imaging method that combines Raman mapping data with microscopy bright-field images to achieve virtual staining of breast cancer tissue sections. We validate our method on various breast tissue sections with different morphologies and biomarker expressions and compare it with the golden standard of histopathological methods. The results demonstrate that our method can effectively distinguish various types and components of tissues, and provide staining images comparable to stained tissue sections. Moreover, our method can improve imaging speed by up to 65 times compared to general spontaneous Raman imaging methods. It is simple, fast, and suitable for clinical applications.

In Situ MOF-74-Pyrolysis-Generated Porous Carbon Supporting Spinel Cu0.15Co2.85O4/C Boosts Ammonium Perchlorate Accelerating Decomposition: Precise Cu Doping Modulating Oxygen Vacancy Concentration.

As one of the main components of solid propellant, ammonium perchlorate (AP) shows slow sluggish decomposition kinetics with unconcentrated heat release. To achieve efficient catalytical decomposition, it is a significant challenge to design reasonable catalyst structure and explore the interaction between catalyst and AP. Herein, a series of porous carbon supported spinel-typed homogeneous heterometallic composites CuxCo3-xO4/C via pyrolysis of MOF-74-Co doped Cu. On basis of precise electronic-structure-tuning through modulating Cu/Co ratio in MOF-74, Cu0.15Co2.85O4/C with 5% Cu-doping featuring oxygen vacancy concentration of 26.25% exhibits the decrease to 261.5 °C with heat release up to 1222.1 J g-1 (456.9 °C and 669.2 J g-1 for pure AP). The detail process of AP accelerated decomposition is approved by TG-DSC-FTIR-MS technique. Density functional theory calculation revealed that in the Cu0.15Co2.85O4/C, the distinctive ability for NH3 catalyzed oxidation assisted with absorption performance of active porous C boosts accelerating AP decomposition. The findings would provide an insight for perceiving and understanding AP catalytic decomposition.

Dual Channel H2O2 Photosynthesis in Pure Water over S-Scheme Heterojunction Cs3PMo12/CC Boosted by Proton and Electron Reservoirs.

Dual channel photo-driven H2O2 production in pure water on small-scale on-site setups is a promising strategy to provide low-concentrated H2O2 whenever needed. This process suffers, however, strongly from the fast recombination of photo-generated charge carriers and the sluggish oxidation process. Here, insoluble Keggin-type cesium phosphomolybdate Cs3PMo12O40 (abbreviated to Cs3PMo12) is introduced to carbonized cellulose (CC) to construct S-scheme heterojunction Cs3PMo12/CC. Dual channel H2O2 photosynthesis from both H2O oxidation and O2 reduction in pure water has been thus achieved with the production rate of 20.1 mmol L-1 gcat. -1 h-1, apparent quantum yield (AQY) of 2.1% and solar-to-chemical conversion (SCC) efficiency of 0.050%. H2O2 accumulative concentration reaches 4.9 mmol L-1. This high photocatalytic activity is guaranteed by unique features of Cs3PMo12/CC, namely, S-scheme heterojunction, electron reservoir, and proton reservoir. The former two enhance the separation of photo-generated charge carriers, while the latter speeds up the torpid oxidation process. In situ experiments reveal that H2O2 is formed via successive single-electron transfer in both channels. In real practice, exposing the reaction system under natural sunlight outdoors successfully results in 0.24 mmol L-1 H2O2. This work provides a key practical strategy for designing photocatalysts in modulating redox half-reactions in photosynthesis.

Oral and oropharyngeal NUT carcinoma: a multicentre screening study of poorly differentiated oral cancer.

BACKGROUND AND AIMS: Nuclear protein testis (NUT) carcinoma (NC) is a rare and highly aggressive tumour characterised by chromosomal rearrangement of the nuclear protein testis family member 1 (NUTM1) gene, also known as the NUT gene. NC occurs mainly in the head and neck, mediastinum and lung. In general, primary NC in the oral cavity is extremely rare and reported sporadically. METHODS: A total of 111 formalin-fixed and paraffin-embedded specimens of poorly differentiated oral and oropharyngeal tumours were collected from 10 hospitals. NUT protein IHC staining was performed on these samples, and fluorescence in-situ hybridisation (FISH) and RNA sequencing detection were further carried out for NUT IHC-positive cases. RESULTS: The expression of NUT protein in tumour cells was detected in five cases (five of 111, 4.5%). The tumours in these cases were located in the oral floor, lip, base of the tongue, gingiva and hard palate. FISH detection results showed BRD4::NUT rearrangement in three patients and a non-BRD4::NUT rearrangement pattern in two patients. RNA sequencing results confirmed BRD4::NUT rearrangement in two cases. CONCLUSIONS: To our knowledge, this is the first and largest retrospective study of oral NC, and we found that NC is easily misdiagnosed as poorly differentiated oral squamous cell carcinoma (SCC) or poorly differentiated carcinoma. The morphology and immunophenotype of four NC cases were similar to SCC, and abrupt keratinisation was observed in three cases. Therefore, it is necessary to detect NUT protein for NC screening in oral malignant tumours with these morphologies, especially for young patients who are more likely to be misdiagnosed with other types of cancer.

The Conjugated/Non-Conjugated Linked Dimer Acceptors Enable Efficient and Stable Flexible Organic Solar Cells.

The fabrication of the flexible devices with excellent photovoltaic performance and stability is critical for the commercialization of organic solar cells (OSCs). Herein, the conjugated dimer acceptor DY-TVCl and the non-conjugated dimer acceptor DY-3T based on the monomer MY-BO are synthesized to regulate the molecular glass transition temperatures (Tg) for improving the morphology stability of active layer films. And the crack onset strain values for the blend films based on dimer acceptors are superior than that of small molecule, which are beneficial for the preparation of flexible devices. Accordingly, the binary device based on PM6:DY-TVCl achieves a maximum power conversion efficiency (PCE) of 18.01%. Meanwhile, the extrapolated T80 (time to reach 80% of initial PCE) lifetimes of the PM6:DY-TVCl-based device and PM6:DY-3T-based device are 3091 and 2227 h under 1-sun illumination, respectively, which are better than that of the PM6:MY-BO-based device (809 h). Furthermore, the flexible devices based on DY-TVCl and DY-3T exhibit the efficiencies of 15.23% and 14.34%, respectively. This work affords a valid approach to improve the stability and mechanical robustness of OSCs, as well as ensuring the reproducibility of organic semiconductors during mass production.

Retrospective comparison of endoscopic transoral and bilateral areolar approaches for thyroglossal cyst resection: a single-centre experience.

PURPOSE: Our study aimed to compare the efficacy, safety, and clinical effect of the transoral approach and the bilateral areolar approach (BAA) for endoscopic thyroglossal duct cyst (TGDC) resection. METHODS: In total, 42 patients who received an endoscopic TGDC resection between January 2019 and May 2022 via a transoral (n = 22) or bilateral areolar (n = 20) approach by a single surgeon were retrospectively enrolled. We collected and compared the following data: patients' demographic data, complication events, operative time, bleeding volume, drainage volume, 6-h postoperative pain scores, length of hospitalisation, resected TGDC size, and cosmetic satisfaction. RESULTS: There were no cases of conversion to a transcervical approach in the two groups. No significant differences were found between the two groups in terms of age, sex, body mass index, complication, bleeding volume, 6-h postoperative pain scores, and TGDC size (all p > 0.05). However, the operative time and patients' cosmetic satisfaction were higher in the transoral group than in the BAA group (all p < 0.05). In addition, the drainage volume and length of hospitalisation in the transoral group were less than those in the BAA group (all p < 0.05). CONCLUSIONS: Both the transoral approach and BAA are safe and reliable; however, the transoral approach is more complex than the BAA and offers better cosmetic satisfaction. Doctors should choose the appropriate surgical procedure based on the patient's condition and preferences.

Influence of screw configuration on reduction and stabilization of simulated complete lateral condylar fracture in equine limbs.

OBJECTIVE: To determine the influence of screw configuration on the reduction and stabilization of simulated complete lateral condylar fracture. STUDY DESIGN: Randomized experimental crossover study. METHODS: A lateral condylar fracture was simulated in 18 cadaver limbs from nine horses. Each limb underwent repair with 4.5 mm diameter cortex screws, tightened to 4 Nm, in a linear and triangular configuration. Computed tomography (CT) of each repair was performed with the limbs in unloaded and loaded conditions. Fracture gaps were measured at the dorsal, palmar, and middle locations of the third metacarpal condyle. Fracture gap measurements were graded 0-4, based on voxels. Following descriptive analysis, a Bayesian network (BN) model was fitted to the data. RESULTS: The median fracture grade was 0 (range: 0-4) for unloaded linear repairs and 2 (0-4) for loaded linear repairs. The median fracture grade was 0 (0-3) for unloaded triangular repairs and 1 (0-3) for loaded triangular repairs. Bayesian network sensitivity analysis showed that the construct configuration reduced the uncertainty in the measured fracture outcome by 0.8%. CONCLUSION: Triangular screw configuration resulted in better fracture reduction and stability in comparison with linear screw configuration. However, the BN sensitivity analysis results showed that the effect of construct configuration on fracture outcome was weak. CLINICAL SIGNIFICANCE: These findings indicate a low probability that triangular repair of lateral condylar fracture will result in improved outcomes, when compared with linear repair.

Preparing healthcare professional students for rural, regional and remote practice: demonstrating the effectiveness of an interprofessional simulation learning experience.

Undertaking an authentic interprofessional simulation experience may be a useful and consistent strategy for healthcare professional students to build competencies required for a rural healthcare context. An observational comparative study design was adopted to evaluate a clinical simulation experience created to develop the interprofessional competencies of a sample of healthcare professional students at a regional university situated on multiple campuses in New South Wales (NSW), Australia. Over 200 students across three campuses of the university were involved in a simulation experience that included four interprofessional activities. Of these students, 189 (89%) agreed to participate in the study. The healthcare professional students who participated in the study were from second year occupational therapy, physiotherapy, and podiatry, and third year speech pathology programs. Retrospective pre and post self-assessed interprofessional collaborative competencies were compared for all students using the revised Interprofessional Collaborative Attainment Survey (ICCAS). Results demonstrated a statistically significant improvement in self-perceived scores using the validated revised ICCAS survey. The findings of this study suggest that carefully designed and authentic interprofessional simulation experiences can facilitate the development of competencies required for effective interprofessional practice, which are necessary for successful rural practice.

DNA Framework-Templated Fabrication of Ultrathin Electroactive Gold Nanosheets.

Generally, two-dimensional gold nanomaterials have unique properties and functions that offer exciting application prospects. However, the crystal phases of these materials tend to be limited to the thermodynamically stable crystal structure. Herein, we report a DNA framework-templated approach for the ambient aqueous synthesis of freestanding and microscale amorphous gold nanosheets with ultrathin sub-nanometer thickness. We observe that extended single-stranded DNA on DNA nanosheets can induce site-specific metallization and enable precise modification of the metalized nanostructures at predefined positions. More importantly, the as-prepared gold nanosheets can serve as an electrocatalyst for glucose oxidase-catalyzed aerobic oxidation, exhibiting enhanced electrocatalytic activity (~3-fold) relative to discrete gold nanoclusters owing to a larger electrochemical active area and wider band gap. The proposed DNA framework-templated metallization strategy is expected to be applicable in a broad range of fields, from catalysis to new energy materials.

Constructing Dynamic Anode/Electrolyte Interfaces Coupled with Regulated Solvation Structures for Long-Term and Highly Reversible Zinc Metal Anodes.

Aqueous zinc ion batteries (AZIBs) show a great potential for next-generation energy storage due to their high safety and high energy density. However, the severe side reactions of zinc negative electrode largely hinder the further application of AZIBs. Herein, trace tris(hydroxymethyl)aminomethane (Tris) additive with rich lone-pair-electrons and zincophilic sites is firstly introduced to achieve long-term and highly reversible Zn plating/stripping. Specifically, Tris not only regulates the solvation structure of Zn2+, but is also adsorbed vertically on the Zn anode surface with a changed coordination intensity during the plating/stripping process of Zn to generate an in situ dynamic adsorption layer for the first time. The dynamic adsorption layer could successively attract the solvated Zn2+ and then promote the de-solvation of the solvated Zn2+ owing to the orientation polarization with regularly-changed applied electric field, the volume rejection effect, and strong intermolecular force towards H2O of the vertically-adsorbed Tris. Therefore, an improved Zn2+-transport kinetics as well as the inhibition of side reactions of Zn anode are successfully realized. Accordingly, the Zn||Zn symmetric cell provides an ultra-long cycle life of 2600 h. Furthermore, the Zn||MnO2 full cell with Tris could demonstrate a high capacity and structural stability for practical applications.

Dual-Strategy Tailoring Molecular Structures of Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transport materials (HTMs) are ideal materials for highly efficient and stable n-i-p perovskite solar cells (PSCs), but most current design strategies for tailoring the molecular structures of HTMs are limited to single strategy. Herein, four HTMs based on dithienothiophenepyrrole (DTTP) core are devised through dual-strategy methods combining conjugate engineering and side chain engineering. DTTP-ThSO with ester alkyl chain that can form six-membered ring by the S⋅⋅⋅O noncovalent conformation lock with thiophene in the backbone shows good planarity, high-quality film, matching energy level and high hole mobility, as well as strong defect passivation ability. Consequently, a remarkable power conversion efficiency (PCE) of 23.3 % with a nice long-term stability is achieved by dopant-free DTTP-ThSO-based PSCs, representing one of the highest values for un-doped organic HTMs based PSCs. Especially, the fill factor (FF) of 82.3 % is the highest value for dopant-free small molecular HTMs-based n-i-p PSCs to date. Moreover, DTTP-ThSO-based devices have achieved an excellent PCE of 20.9 % in large-area (1.01 cm2) devices. This work clearly elucidates the structure-performance relationships of HTMs and offers a practical dual-strategy approach to designing dopant-free HTMs for high-performance PSCs.

Micron-Scale Fabrication of Ultrathin Amorphous Copper Nanosheets Templated by DNA Scaffolds.

Two-dimensional (2D) amorphous materials could outperform their crystalline counterparts toward various applications because they have more defects and reactive sites and thus could exhibit a unique surface chemical state and provide an advanced electron/ion transport path. Nevertheless, it is challenging to fabricate ultrathin and large-sized 2D amorphous metallic nanomaterials in a mild and controllable manner due to the strong metallic bonds between metal atoms. Here, we reported a simple yet fast (10 min) DNA nanosheet (DNS)-templated method to synthesize micron-scale amorphous copper nanosheets (CuNSs) with a thickness of 1.9 ± 0.4 nm in aqueous solution at room temperature. We demonstrated the amorphous feature of the DNS/CuNSs by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Interestingly, we found that they could transform to crystalline forms under continuous electron beam irradiation. Of note, the amorphous DNS/CuNSs exhibited much stronger photoemission (∼62-fold) and photostability than dsDNA-templated discrete Cu nanoclusters due to the elevation of both the conduction band (CB) and valence band (VB). Such ultrathin amorphous DNS/CuNSs hold great potential for practical applications in biosensing, nanodevices, and photodevices.

Nonclassical autophagy activation pathways are essential for production of infectious Influenza A virus in vitro.

Autophagy is a critical mechanism deployed by eukaryotic cells in response to stress, including viral infection, to boost the innate antimicrobial responses. However, an increasing number of pathogens hijack the autophagic machinery to facilitate their own replication. Influenza A virus (IAV), responsible for several global pandemics, has an intricate dependence on autophagy for successful replication in mammalian cells. To elucidate key chokepoints in the host stress responses facilitating IAV replication, we constructed a meta-transcriptome of IAV and host gene expression dynamics during early (1-3 hpi), mid (4-6 hpi), and late (8-12 hpi) stages of the viral replication cycle at two multiplicities of infection (MOI): 1 and 5. We supplemented the global transcriptome study with phosphoproteomic analysis of stress-activated protein kinase (SAPK/JNK) signaling in lung carcinoma (predominantly used as an in vitro model of IAV replication) and normal human bronchial epithelial cells. We report significant differences in the activation profiles of autophagy regulating genes upon IAV infection at the two MOI as well as divergent dependence on ULK1 signaling within the normal and cancer cells. Regardless of the cell model, JNK-Thr187 signaling was crucial for the production of infectious viral particles.

Combined Morphological and Spectroscopic Diagnostic of HER2 Expression in Breast Cancer Tissues Based on Label-Free Surface-Enhanced Raman Scattering.

Breast cancer is the most commonly diagnosed cancer type worldwide. Overexpression of human epidermal growth factor receptor 2 (HER2) is an important subtype of breast cancer and results in an increased risk of recurrence and metastasis in patients. At present, immunohistochemistry (IHC) is used to detect the expression of HER2 in breast cancer tissues as the golden standard. However, IHC has some shortcomings, such as large subjective impact, long time consumption, expensive reagents, etc. In this paper, a combined morphological and spectroscopic diagnostic method based on label-free surface-enhanced Raman scattering (SERS) for HER2 expression in breast cancer is proposed. It can not only quantitively detect HER2 expression in breast cancer tissues by spectroscopic measurements but also give morphological images reflecting the distribution of HER2 in tissues. The results show that the consistency between this method and IHC is 95% and achieves the annotation of tumor regions on tissue sections. This method is time-consuming, quantifiable, intuitive, scalable, and easy to understand. Combined with deep learning approaches, it is expected to promote the development of clinical detection and diagnosis technology for breast cancer and other cancers.

Constructing Ru@C3 N4 /Cu Tandem Electrocatalyst with Dual-Active Sites for Enhanced Nitrate Electroreduction to Ammonia.

Electroreduction of nitrate to ammonia reaction (NO3 - RR) is considered as a promising carbon-free energy technique, which can eliminate nitrate from waste-water also produce value-added ammonia. However, it remains a challenge for achieving satisfied ammonia selectivity and Faraday efficiency (FE) due to the complex multiple-electron reduction process. Herein, a novel Tandem electrocatalyst that Ru dispersed on the porous graphitized C3 N4 (g-C3 N4 ) encapsulated with self-supported Cu nanowires (denoted as Ru@C3 N4 /Cu) for NO3 - RR is presented. As expected, a high ammonia yield of 0.249 mmol h-1  cm-2 at -0.9 V and high FENH3 of 91.3% at -0.8 V versus RHE can be obtained, while achieving excellent nitrate conversion (96.1%) and ammonia selectivity (91.4%) in neutral solution. In addition, density functional theory (DFT) calculations further demonstrate that the superior NO3 - RR performance is mainly resulted from the synergistic effect between the Ru and Cu dual-active sites, which can significantly enhance the adsorption of NO3 - and facilitate hydrogenation, as well as suppress the hydrogen evolution reaction, thus lead to highly improved NO3 - RR performances. This novel design strategy would pave a feasible avenue for the development of advanced NO3 - RR electrocatalysts.

LncRNA AGAP2 antisense RNA 1 stabilized by insulin-like growth factor 2 mRNA binding protein 3 promotes macrophage M2 polarization in clear cell renal cell carcinoma through regulation of the microRNA-9-5p/THBS2/PI3K-Akt pathway.

BACKGROUND: Increasing evidence highlights the potential role of long non-coding RNAs (lncRNAs) in the biological behaviors of renal cell carcinoma (RCC). Here, we explored the mechanism of AGAP2-AS1 in the occurrence and development of clear cell RCC (ccRCC) involving IGF2BP3/miR-9-5p/THBS2. METHODS: The expressions of AGAP2-AS1, IGF2BP3, miR-9-5p, and THBS2 and their relationship were analyzed by bioinformatics. The targeting relationship between AGAP2-AS1 and miR-9-5p and between miR-9-5p and THBS2 was evaluated with their effect on cell biological behaviors and macrophage polarization assayed. Finally, we tested the effect of AGAP2-AS1 on ccRCC tumor formation in xenograft tumors. RESULTS: IGF2BP3 could stabilize AGAP2-AS1 through m6A modification. AGAP2-AS1 was highly expressed in ccRCC tissues and cells. The lentivirus-mediated intervention of AGAP2-AS1 induced malignant behaviors of ccRCC cells and led to M2 polarization of macrophages. In addition, THBS2 promoted M2 polarization of macrophages by activating the PI3K/AKT signaling pathway. AGAP2-AS1 could directly bind with miR-9-5p and promote the expression of THBS2 downstream of miR-9-5p. These results were further verified by in vivo experiments. CONCLUSION: AGAP2-AS1 stabilized by IGF2BP3 competitively binds to miR-9-5p to up-regulate THBS2, activating the PI3K/AKT signaling pathway and inducing macrophage M2 polarization, thus facilitating the development of RCC.

Novel Pyrimidine-Based Iridium Complexes with Bulky Charge-Carrier Groups as Dopants for Highly Efficient Green Polymer Light-Emitting Diodes.

Two new pyrimidine-based iridium complexes with triphenylamine and tetraphenylsilane, namely (TPAPr)2 IrAcac and (TPSPr)2 IrAcac, were fully synthesized and characterized. Both of the targeted iridium complexes exhibit excellent thermal stability and high photoluminescence quantum yields. Compared to (TPAPr)2 IrAcac, (TPSPr)2 IrAcac achieved its highest PLQY and current efficiency (CE) at higher dopant concentration probably because of its bulky tetraphenylsilane group, which can effectively suppress the concentration quenching. However, according to DFT studies, (TPSPr)2 IrAcac shows faster non-radiative transitions due to the presence of more excited-state distortions than (TPAPr)2 IrAcac. As a result, Green phosphorescent polymer light-emitting diodes (PLEDs) containing (TPAPr)2 IrAcac and (TPSPr)2 IrAcac as dopants exhibit exceptional device performance with peak CE values of 38.24 and 36.06 cd A-1 , respectively. (TPAPr)2 IrAcac exhibited a superior efficiency than (TPSPr)2 IrAcac because of its high Φp , low RMSD value, and efficient energy transfer from the host to the guest. More importantly, the PLEDs based on (TPAPr)2 IrAcac and (TPSPr)2 IrAcac show stable phosphorescent emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.313, 0.497) and (0.299, 0.483), respectively. This work points out a viable method for creating phosphorescent iridium complexes based on pyrimidine for high-efficiency organic light-emitting diodes (OLEDs).

Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiW9Co3@UiO-67-NH2 Deciding High Stability and Photocatalytic CO2 Reduction Performance.

Merging metal-organic frameworks (MOFs) and polyoxometalates (POMs) into heterogeneous heterojunction photocatalysts through in situ encapsulation is an effective approach to suppress the leachability of POMs and enhance their electron supply. The heterointerfacial connection in POMs@MOFs directly determines the performance of stability and charge separation, and the suited interaction between MOFs and POMs for POMs@MOFs heterojunctions photocatalyst is of vital importance. Here, a distinctive Keggin-type POM [(n-C4H9)N]10[SiW9Co3 (H2O)3O37]·17H2O (SiW9Co3) with near-total visible region absorption, narrow band gap of 2.23 eV, and powerful electron supply activity was prepared and tightly immobilized in the cavities of UiO-67-NH2 and UiO-68-NH2 to construct two Z-scheme heterojunctions SiW9Co3@UiO-67-NH2 and SiW9Co3@UiO-68-NH2, which were used for photocatalytic reduction of CO2 to CO. Their compositions, structures, and energy band features were fully characterized by a series of tests including XRD, FT-IR, SEM, XPS, UV-vis-DRS, UPS, and so forth. SiW9Co3@UiO-67-NH2 showed optimal photocatalytic performance with an excellent CO yield of 153.3 µmol-1·g-1·h-1 and a selectivity of 100%, which is 3.3-fold higher than that of SiW9Co3@UiO-68-NH2 and far superior to most reported POM-based heterojunctions. Comprehensive investigations with extensive photoelectric characterizations and microcalorimetric experiments demonstrated that the exceptional photocatalytic performances of SiW9Co3@UiO-67-NH2 could be attributed to the fact that (i) strong host-guest interactions were formed due to the well-matched dimensions between SiW9Co3 cluster and MOF cavity, which generated an intimate heterointerface to effectively accelerate interface electron transfer; (ii) the intimate heterointerface promoted SiW9Co3 to yield multielectron supply for efficient interfacial carrier neutralization owing to its donor-acceptor structure and narrow band gap. Additionally, the excellent durability of SiW9Co3@UiO-67-NH2 was also supported by the solidly locked SiW9Co3 and a stable MOF framework.

A Stable Triphenylamine-Based Zn(II)-MOF for Photocatalytic H2 Evolution and Photooxidative Carbon-Carbon Coupling Reaction.

Efficient charge transfer has always been a challenge in heterogeneous MOF-based photoredox catalysis due to the poor electrical conductivity of the MOF photocatalyst, the toilless electron-hole recombination, and the uncontrollable host-guest interactions. Herein, a propeller-like tris(3'-carboxybiphenyl)amine (H3TCBA) ligand was synthesized to fabricate a 3D Zn3O cluster-based Zn(II)-MOF photocatalyst, Zn3(TCBA)2(µ3-H2O)H2O (Zn-TCBA), which was applied to efficient photoreductive H2 evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of N-aryl-tetrahydroisoquinolines and nitromethane. In Zn-TCBA, the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes Zn-TCBA to exhibit a broad visible-light absorption with a maximum absorption edge of 480 nm but also causes special phenyl plane twists with dihedral angles of 27.8-45.8° through the coordination to Zn nodes. The semiconductor-like Zn clusters and the twisted TCBA3- antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render Zn-TCBA a good photocatalytic H2 evolution efficiency of 27.104 mmol·g-1·h-1 in the presence of [Co(bpy)3]Cl2 under visible-light illumination, surpassing many non-noble-metal MOF systems. Moreover, the positive enough excited-state potential of 2.03 V and the semiconductor-like characteristics of Zn-TCBA endow Zn-TCBA with double oxygen activation ability for photocatalytic oxidation of N-aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of Zn-TCBA and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.