Localized nitride strategy to construct interfacial and electronic modulated WO3/WN nanoparticles for superior lithium-ion storage.

The interfacial effect is important for the tungsten trioxide (WO3)-based anode to achieve superior lithium-ion storage performance. Herein, the interfacial effect was constructed by in-situ surface direct nitridation reaction at 600 â„ƒ for 30 min of the as-synthesis WO3 nanoparticles (WO3/WN). X-ray photoelectron spectroscopy (XPS) analysis confirms evident chemical interaction between WO3 and WN via the interfacial covalent bond (WON). This WO3/WN anode shows a distinct interfacial effect for an efficient interatomic electron migration. Electrochemical kinetic analysis shows enhanced pseudocapacitance contribution. The galvanostatic intermittent titration technique (GITT) result demonstrates improved charge transfer kinetics. Ex-situ X-ray diffraction (XRD) analysis reveals the reversible oxidation and reduction reaction of the WO3/WN anode. The density functional theory (DFT) result shows that the evident interfacial bonding effect can enhance the electrochemical reaction kinetics of the WO3/WN anode. The discharge capacity can reach up to 546.9 mA h g-1 at 0.1 A g-1 after 200 cycles. After 2000 cycles, the capacity retention is approximately 85.97 % at 1.0 A g-1. In addition, the WO3/WN full cell (LiFePO4/C//WO3/WN) demonstrates excellent rate capability and capacity retention ratio. This in-situ surface nitridation strategy is an effective solution for designing an oxide-based anode with good electrochemical performance and beyond.

Core-Shell Engineered Fillers Overcome the Electrical-Thermal Conductance Trade-Off.

The rapid development of modern electronic devices increasingly requires thermal management materials with controllable electrical properties, ranging from conductive and dielectric to insulating, to meet the needs of diverse applications. However, highly thermally conductive materials usually have a high electrical conductivity. Intrinsically highly thermally conductive, but electrically insulating materials are still limited to a few kinds of materials. To overcome the electrical-thermal conductance trade-off, here, we report a facile Pechini-based method to prepare multiple core (metal)/shell (metal oxide) engineered fillers, such as aluminum-oxide-coated and beryllium-oxide-coated Ag microspheres. In contrast to the previous in situ growth method which mainly focused on small-sized spheres with specific coating materials, our method combined with ultrafast joule heating treatment is more versatile and robust for varied-sized, especially large-sized core-shell fillers. Through size compounding, the as-synthesized core-shell-filled epoxy composites exhibit high isotropic thermal conductivity (∼3.8 W m-1 K-1) while maintaining high electrical resistivity (∼1012 Ω cm) and good flowability, showing better heat dissipation properties than commercial thermally conductive packaging materials. The successful preparation of these core-shell fillers endows thermally conductive composites with controlled electrical properties for emerging electronic package applications, as demonstrated in circuit board and battery thermal management.

Advances and challenges in neuroimaging-based pain biomarkers.

Identifying neural biomarkers of pain has long been a central theme in pain neuroscience. Here, we review the state-of-the-art candidates for neural biomarkers of acute and chronic pain. We classify these potential neural biomarkers into five categories based on the nature of their target variables, including neural biomarkers of (1) within-individual perception, (2) between-individual sensitivity, and (3) discriminability for acute pain, as well as (4) assessment and (5) prospective neural biomarkers for chronic pain. For each category, we provide a synthesized review of candidate biomarkers developed using neuroimaging techniques including functional magnetic resonance imaging (fMRI), structural magnetic resonance imaging (sMRI), and electroencephalography (EEG). We also discuss the conceptual and practical challenges in developing neural biomarkers of pain. Addressing these challenges, optimal biomarkers of pain can be developed to deepen our understanding of how the brain represents pain and ultimately help alleviate patients' suffering and improve their well-being.

Rheumatoid arthritis and gliostatin: a two-sample Mendelian randomization analysis and RT-PCR validation.

BACKGROUND: Rheumatoid arthritis (RA) is a chronic systemic autoimmune disease of unknown etiology. Cuproptosis, a novel form of cell death, is characterized by cytotoxicity originating from copper ions. To date, the relationship between cuproptosis-related gene gliostatin (GLS) and RA. METHODS: All raw data were retrieved from the Gene Expression Omnibus (GEO) public database. The expression level of genes between RA and healthy samples was evaluated to identify differentially expressed genes. Then, LASSO regression was used to screen disease signature genes, and a nomogram was constructed based on five hub genes to predict disease scores. Validation experiments were performed using quantitative real-time PCR (qRT-PCR) to detect the most significant CRGs. Finally, the causal relationship between GLS and RA was analyzed through Mendelian randomization methodology. RESULTS: Five differentially expressed CRGs (NLRP3, ATP7A, MTF1, GLS, and DBT) were identified between normal and RA samples, all of which were validated as disease-specific genes through LASSO regression analysis. Meanwhile, the nomogram demonstrated a positive correlation between RA and the expression of GLS. Furthermore, q-PCR revealed that the expression level of GLS was higher in RA patients compared to those in the control group. Taken together, a causal relationship between GLS and RA was corroborated through Mendelian randomization. CONCLUSION: GLS, a cuproptosis-related gene, is closely associated with RA and plays a significant role in its diagnosis. Key Points • The causal relationship between GLS and RA is proved by Mendelian randomization.

Applications of mixture methods in epidemiological studies investigating the health impact of persistent organic pollutants exposures: a scoping review.

BACKGROUND: Persistent organic pollutants (POPs) are environmental chemicals characterized by long half-lives in nature and human bodies, posing significant health risks. The concept of the exposome, encompassing all lifetime environmental exposures, underscores the importance of studying POP as mixtures rather than in isolation. The increasing body of evidence on the health impacts of POP mixtures necessitates the proper application of statistical methods. OBJECTIVES: We aimed to summarize studies on the overall effects of POP mixtures, identify patterns in applications of mixture methods-statistical methods for investigating the association of mixtures-and highlight current challenges in synthesizing epidemiologic evidence of POP mixtures on health effects as illustrated through a case study. METHODS: We conducted a systematic literature search on PubMed and Embase for epidemiological studies published between January 2011 and April 2023. RESULTS: We included 240 studies that met our eligibility criteria. 126 studies focused on per- and polyfluoroalkyl substances (PFAS) mixtures only, while 40 analyzed three or more classes of POPs in mixture analyses. We identified 23 unique mixture methods used to estimate the overall effects of POP mixtures, with Bayesian Kernel Machine Regression (BKMR), a type of response-surface modeling, being the most common. Additionally, 22.9% of studies used a combination of methods, including response-surface modeling, index modeling, dimension reduction, and latent variable models. The most extensively explored health outcome category was body weight and birth sizes (n = 43), and neurological outcomes (n = 41). In the case study of PFAS mixtures and birth weight, 12 studies showed negative associations, while 4 showed null results, and 2 showed positive associations. IMPACT STATEMENT: This scoping review consolidates the existing literature on the overall effects of POP mixtures using statistical methods. By providing a comprehensive overview, our study illuminates the present landscape of knowledge in this field and underscores the methodological hurdles prevalent in epidemiological studies focused on POP mixtures. Through this analysis, we aim to steer future research directions, fostering a more nuanced comprehension of the intricate dynamics involved in assessing the health effects of POP mixtures. Our work stands as a significant contribution to the ongoing exploration of the chemical exposome.

Multimodal Image Confidence: A Novel Method for Tumor and Organ Boundary Representation.

The indistinct boundaries of tumors and organs at risk in medical images present significant challenges in treatment planning and other tasks in radiation therapy. This study introduces an innovative analytical algorithm called multimodal image confidence (MMC), which leverages the complementary strengths of various multimodal medical images to assign a confidence measure to each voxel within the region of interest (ROI). MMC enables the generation of modality-specific ROI-enhanced images, providing a detailed depiction of both the boundaries and internal features of the ROI. By employing an interpretable mathematical model that propagates voxel confidence based on intervoxel correlations, MMC circumvents the need for model training, distinguishing it from deep learning-based methods. The alogorithm was evaluated qualitatively and quantitatively on 156 nasopharyngeal carcinoma cases and 1251 glioma cases. Qualitative assessments demonstrated MMC's accuracy in delineating lesion boundaries as well as capturing internal tumor characteristics. Quantitative analyses further revealed strong concordance between MMC and manual delineations. This study presents a cutting-edge algorithm for identifying and illustating ROI boundaries using multimodal 3D medical images. The versatility of the proposed method extends to both targets and organs at risk across various anatomic sites and multiple image modalities, enhancing its potential for accurate delineation of critical structures andmany image-related tasks in radiaton therapy and other fields.

Shading and Water Addition Alleviate the Elemental Limitations of the Early Restoration Community in a Stressful Environment.

Shading and water addition are essential management measures to improve seed germination and early seedling survival; however, little is known about their effects on leaf stoichiometry and nutrient status. We established 90 plant communities with shading and water addition gradients on a rocky hill; leaves of their dominant woody plant species were collected to measure elemental concentrations, and then, stoichiometric variation and nutrient status were analysed. The results showed that the overall effects of shading and water addition significantly altered the concentrations and ratios of nutrient elements; shading largely affected leaf K and P, while water addition mainly affected leaf N and P. The interactions between shading and water addition were significant for most species but disappeared at the community level. Consequently, the nutrient status in leaves was improved by promoting the concentrations and balances of nutrient elements. However, the responses to shading and water addition were marked by species-specific differences, with some plants forming a sensitive group and others distinguished by conservatism. Our findings show that management of the physical environment could improve nutrient element utilization in leaves and alleviate the nutrient limitations. For our site conditions, mild shading (25-35%) and adequate water addition (30 L·m-2) in the early stage of vegetation restoration is recommended to advance community assembly by improving nutrient physiology, directly diminishing the stress of water scarcity and excessive irradiation. These findings explore the underlying mechanisms of shading and water addition that could promote community development and provide guidance for restoration practice.

Efficient production of pullulan by Aureobasidium pullulans using a multi-objective optimization strategy with orthogonal experimental design coupling artificial neural network and genetic algorithm.

Efficient pullulan production has long been a central research focus. This study used maltodextrin as the carbon source for pullulan production by Aureobasidium pullulans fermentation. A hybrid optimization approach, integrating orthogonal experimental design (OED), backpropagation artificial neural network (BP-ANN), and elite strategy non-dominated sequential genetic algorithm-II (NSGA-II), was developed. Range analysis based on OED revealed that MgSO4·7H2O significantly affects production but less impacts molecular weight, while pH notably influences molecular weight with a lesser effect on production, underscoring the need for multi-objective optimization. The BP-ANN model showed strong predictive capabilities, with goodness-of-fit values of 0.984 and 0.980 for production and molecular weight, respectively. Using this model as the fitness function for the optimization algorithm enhanced efficiency. Taking cost factors into account, the BP-ANN-NSGA-II algorithm identified the optimal fermentation medium conditions, resulting in a 6.89 % increase in production, a 368.97 % increase in molecular weight, and a 42.49 % reduction in cost. The maximum comprehensive optimization efficiency is 63.73 %, and the multi-objective optimization is better than the single objective optimization. This method significantly guides the improvement of pullulan fermentation optimization efficiency.

Concurrent chemoradiotherapyof different radiation doses and different irradiation fields for locally advanced thoracic esophageal squamous cell carcinoma: A randomized, multicenter, phase III clinical trial.

BACKGROUND: Concurrent chemoradiotherapy (CCRT) is the standard treatment for locally advanced esophageal squamous cell carcinoma (ESCC). However, the optimal radiotherapy regimen, particularly in terms of total dose and planned range of irradiation field, remains unclear. This phase III clinical trial aimed to compare the survival benefits between different radiation doses and different target fields. METHODS: This trial compared two aspects of radiation treatment, total dose and field, using a two-by-two factorial design. The high-dose (HD) group received 59.4 Gy radiation, and the standard-dose (SD) group received 50.4 Gy. The involved field irradiation (IFI) group and elective nodal irradiation (ENI) group adopted different irradiation ranges. The participants were assigned to one of the four groups (HD+ENI, HD+IFI, SD+ENI and SD+IFI). The primary endpoint was overall survival (OS), and the secondary endpoints included progression-free survival (PFS). The synergy indexwas used to measure the interaction effect between dose and field. RESULTS: The interaction analysis did not reveal significant synergistic effects between the dose and irradiation field. In comparison to the target field, patients in IFI or ENI showed similar OS (hazard ratio [HR] = 0.99, 95% CI: 0.80-1.23, p = 0.930) and PFS (HR = 1.02, 95% CI: 0.82-1.25). The HD treatment did not show significantly prolonged OS compared with SD (HR = 0.90, 95% CI: 0.72-1.11, p = 0.318), but it suggested improved PFS (25.2 months to 18.0 months). Among the four groups, the HD+IFI group presented the best survival, while the SD+IFI group had the worst prognosis. No significant difference in the occurrence of severe adverse events was found in dose or field comparisons. CONCLUSIONS: IFI demonstrated similar treatment efficacy to ENI in CCRT of ESCC. The HD demonstrated improved PFS, but did not significantly improve OS. The dose escalation based on IFI (HD+IFI) showed better therapeutic efficacy than the current recommendation (SD+ENI) and is worth further validation.

Enhancing Defect-Induced Dipole Polarization Strategy of SiC@MoO3 Nanocomposite Towards Electromagnetic Wave Absorption.

Defect engineering in transition metal oxides semiconductors (TMOs) is attracting considerable interest due to its potential to enhance conductivity by intentionally introducing defects that modulate the electronic structures of the materials. However, achieving a comprehensive understanding of the relationship between micro-structures and electromagnetic wave absorption capabilities remains elusive, posing a substantial challenge to the advancement of TMOs absorbers. The current research describes a process for the deposition of a MoO3 layer onto SiC nanowires, achieved via electro-deposition followed by high-temperature calcination. Subsequently, intentional creation of oxygen vacancies within the MoO3 layer was carried out, facilitating the precise adjustment of electromagnetic properties to enhance the microwave absorption performance of the material. Remarkably, the SiC@MO-t4 sample exhibited an excellent minimum reflection loss of - 50.49 dB at a matching thickness of 1.27 mm. Furthermore, the SiC@MO-t6 sample exhibited an effective absorption bandwidth of 8.72 GHz with a thickness of 2.81 mm, comprehensively covering the entire Ku band. These results not only highlight the pivotal role of defect engineering in the nuanced adjustment of electromagnetic properties but also provide valuable insight for the application of defect engineering methods in broadening the spectrum of electromagnetic wave absor ption effectiveness. SiC@MO-t samples with varying concentrations of oxygen vacancies were prepared through in-situ etching of the SiC@MoO3 nanocomposite. The presence of oxygen vacancies plays a crucial role in adjusting the band gap and local electron distribution, which in turn enhances conductivity loss and induced polarization loss capacity. This finding reveals a novel strategy for improving the absorption properties of electromagnetic waves through defect engineering.

PFHpA alters lipid metabolism and increases the risk of metabolic dysfunction-associated steatotic liver disease in youth-a translational research framework.

To address the growing epidemic of liver disease, particularly in pediatric populations, it is crucial to identify modifiable risk factors for the development and progression of metabolic dysfunction-associated steatotic liver disease (MASLD). Per- and polyfluoroalkyl substances (PFAS) are persistent ubiquitous chemicals and have emerged as potential risk factors for liver damage. However, their impact on the etiology and severity of MASLD remains largely unexplored in humans. This study aims to bridge the gap between human and in vitro studies to understand how exposure to perfluoroheptanoic acid (PFHpA), one of the emerging PFAS replacements which accumulates in high concentrations in the liver, contributes to MASLD risk and progression. First, we showed that PFHpA plasma concentrations were significantly associated with increased risk of MASLD in obese adolescents. Further, we examined the impact of PFHpA on hepatic metabolism using 3D human liver spheroids and single-cell transcriptomics to identify major hepatic pathways affected by PFHpA. Next, we integrated the in vivo and in vitro multi-omics datasets with a novel statistical approach which identified signatures of proteins and metabolites associated with MASLD development triggered by PFHpA exposure. In addition to characterizing the contribution of PFHpA to MASLD progression, our study provides a novel strategy to identify individuals at high risk of PFHpA-induced MASLD and develop early intervention strategies. Notably, our analysis revealed that the proteomic signature exhibited a stronger correlation between both PFHpA exposure and MASLD risk compared to the metabolomic signature. While establishing a clear connection between PFHpA exposure and MASLD progression in humans, our study delved into the molecular mechanisms through which PFHpA disrupts liver metabolism. Our in vitro findings revealed that PFHpA primarily impacts lipid metabolism, leading to a notable increase of lipid accumulation in human hepatocytes after PFHpA exposure. Among the pathways involved in lipid metabolism in hepatocytes, regulation of lipid metabolism by PPAR-a showed a remarkable activation. Moreover, the translational research framework we developed by integrating human and in vitro data provided us biomarkers to identify individuals at a high risk of MASLD due to PFHpA exposure. Our framework can inform policies on PFAS-induced liver disease and identify potential targets for prevention and treatment strategies.

Clinical and genetic characteristics of Chinese pediatric and adult patients with hereditary spherocytosis.

OBJECTIVE: This study aimed to investigate the clinical features, pathogenic gene variants, and potential genotype-phenotype correlations in Chinese patients with hereditary spherocytosis (HS). METHODS: Retrospective analysis of clinical data and molecular genetic characteristics was conducted on patients diagnosed with HS at Jiangxi Provincial Children's Hospital, the Second Affiliated Hospital of Nanchang University, Pingxiang People's Hospital and The Third People's Hospital of Jingdezhen between November 2017 and June 2023. Statistical analyses were performed to compare and analyze the red blood cell (RBC), hemoglobin (HB), mean corpuscular volume (MCV), mean corpuscular hemoglobin (MCH), and mean corpuscular hemoglobin concentration (MCHC) data between and within groups based on different mutations and age groups (< 14 and ≥ 14 years). RESULTS: A total of 34 HS patients were included in this study, comprising 22 children (64.70%) and 12 adults (35.30%). The probands who underwent genetic testing were derived from 34 unrelated families. Thirty-two variants were tested and 9 of them are novel. Eighteen cases had ANK1 variants, 15 had SPTB variants, and 1 had SLC4A1 variant. 25 patients performed core family members underwent genetic testing, 17 (68.0%, 17/25) were de novo, 5 (20.0%, 5/25) were maternally inherited, and 3 (12.0%, 3/25) were paternally inherited. ANK1-HS patients exhibited more severe anemia compared to cases with SPTB-HS, showing lower levels of RBC and HB (P < 0.05). Anemia was more severe in patients diagnosed in childhood than in those diagnosed in adulthood. Within the ANK1-HS group, MCH levels in adult patients was significantly higher than those in children (P < 0.05), while there were no significant differences in RBC, HB, MCV, and MCHC levels between two groups. Adult patients with SPTB-HS had significantly higher levels of RBC, HB, and MCH than pediatric patients (P < 0.05), while MCV and MCHC levels showed no significant statistical differences. CONCLUSION: This study conducted a comparative analysis of phenotypic characteristics and molecular genetics in adult and pediatric patients diagnosed with HS, confirming that pediatric ANK1-HS patients exhibit a more severe anemic phenotype compared to SPTB-HS patients, while the severity of HS in adults does not significantly differ between different causative genes.

Rapid and sustained response to luspatercept and eltrombopag combined treatment in one case of clonal cytopenias of undetermined significance with prior failure to cyclosporin and androgen therapy: a case report.

Clonal cytopenia of undetermined significance (CCUS) has the characteristics of high-risk transformation into myelodysplastic syndromes. At present, there are few effective treatments for CCUS, and there is no consensus or evidence-based recommendation. We present a case demonstrating a rapid, significant and sustained response to combined treatment with luspatercept and eltrombopag, following the failure of cyclosporin and androgen therapy. Even after discontinuing luspatercept for 10 months, trilineage haematopoiesis remained normal with the use of cyclosporin and other haematopoietic stimulants. This case suggests that the inhibition of transforming growth factor-ß could potentially have an immunomodulatory effect, thereby promoting the recovery of haematopoietic function. Luspatercept, along with Acalabrutinib or Cyclosporine, may synergistically stimulate haematopoiesis.

Association of effective dose to immune cells and vertebral marrow dose with hematologic toxicity during neoadjuvant chemoradiotherapy in esophageal squamous cell carcinoma.

BACKGROUND: To explore the correlation between effective dose to immune cells (EDIC) and vertebral bone marrow dose and hematologic toxicity (HT) for esophageal squamous cell carcinoma (ESCC) during neoadjuvant chemoradiotherapy (nCRT). METHODS: The study included 106 ESCC patients treated with nCRT. We collected dosimetric parameters, including vertebral body volumes receiving 10-40 Gy (V10, V20, V30, V40) and EDIC and complete blood counts. Associations of the cell nadir and dosimetric parameters were examined by linear and logistic regression analysis. The receiver operating characteristic (ROC) curves were used to determine the cutoff values for the dosimetric parameters. RESULTS: During nCRT, the incidence of grade 3-4 lymphopenia, leukopenia, and neutropenia was 76.4%, 37.3%, and 37.3%, respectively. Patients with EDIC ≤ 4.63 Gy plus V10 ≤ 140.3 ml were strongly associated with lower risk of grade 3-4 lymphopenia (OR, 0.050; P < 0.001), and patients with EDIC ≤ 4.53 Gy plus V10 ≤ 100.9 ml were strongly associated with lower risk of grade 3-4 leukopenia (OR, 0.177; P = 0.011), and patients with EDIC ≤ 5.79 Gy were strongly associated with lower risk of grade 3-4 neutropenia (OR, 0.401; P = 0.031). Kaplan-Meier analysis showed that there was a significant difference among all groups for grade 3-4 lymphopenia, leukopenia, and neutropenia (P < 0.05). CONCLUSION: The dose of vertebral bone marrow irradiation and EDIC were significantly correlated with grade 3-4 leukopenia and lymphopenia, and EDIC was significantly correlated with grade 3-4 neutropenia. Reducing vertebral bone marrow irradiation and EDIC effectively reduce the incidence of HT.

Tailoring d-p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics.

The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d-p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co-substituted Ni3Se4 can hold the optimal d-p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH- adsorption-desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59 eV, matching well with the theoretical calculations). Coupling with the lower OH- diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200 times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery-type electrodes from a novel perspective of orbital-scale manipulation.

Feasibility and safety of contrast-enhanced magnetic resonance-guided adaptive radiotherapy for upper abdominal tumors: A preliminary exploration.

This study investigates the use of contrast-enhanced magnetic resonance (MR) in MR-guided adaptive radiotherapy (MRgART) for upper abdominal tumors. Contrast-enhanced T1-weighted MR (cT1w MR) using half doses of gadoterate was used to guide daily adaptive radiotherapy for tumors poorly visualized without contrast. The use of gadoterate was found to be feasible and safe in 5-fraction MRgART and could improve the contrast-to-noise ratio of MR images. And the use of cT1w MR could reduce the interobserver variation of adaptive tumor delineation compared to plain T1w MR (4.41 vs. 6.58, p < 0.001) and T2w MR (4.41 vs. 7.42, p < 0.001).

Degree of disorder-regulated ion transport through amorphous monolayer carbon.

Nanopore technology, re-fueled by two-dimensional (2D) materials such as graphene and MoS2, controls mass transport by allowing certain species while denying others at the nanoscale and has a wide application range in DNA sequencing, nano-power generation, and others. With their low transmembrane transport resistance and high permeability stemming from their ultrathin nature, crystalline 2D materials do not possess nanoscale holes naturally, thus requiring additional fabrication to create nanopores. Herein, we demonstrate that nanopores exist in amorphous monolayer carbon (AMC) grown at low temperatures. The size and density of nanopores can be tuned by the growth temperature, which was experimentally verified by atomic images and further corroborated by kinetic Monte Carlo simulation. Furthermore, AMC films with varied degrees of disorder (DOD) exhibit tunable transmembrane ionic conductance over two orders of magnitude when serving as nanopore membranes. This work demonstrates the DOD-tuned property in amorphous monolayer carbon and provides a new candidate for modern membrane science and technology.

Mechanistic insight into the synergy between platinum cluster and indium particle dual cocatalysts for enhanced photocatalytic water splitting.

Photocatalytic H2 production is envisioned as a promising pillar of sustainable energy conversion system to address the energy crisis and environmental issues but still challenging. Herein, a strategy is proposed to design a dual-metal cocatalysts consisting of Pt nanoclusters (Pt NCs) and In nanoparticles (In NPs) anchored on polymeric carbon nitride (Pt-In/CN) for boosting photocatalytic water splitting. As expected, the designed Pt-In/CN photocatalyst exhibits an impressive H2 production rate of 6.49 mmol·h-1·g-1 with an apparent quantum yield (AQY) of 33.56 % at 400 nm, which is 2.8- and 11.2-fold higher than those of the Pt/CN and In/CN, respectively. Combining experimental characterization with theoretical calculation demonstrates the synergistic mechanisms underpinning the enhanced photocatalytic activity. The Pt NCs and In NPs serve as photogenerated electron and hole trapping sites, respectively, which achieves the spatial separation of charge carriers and induces the polarized surface charge distribution, thus fostering optimal adsorption behavior of intermediates. More importantly, the p-block In NPs modulate the electronic microenvironment of Pt NCs to attenuate the adsorption behavior of H* intermediates for accelerated H2 evolution kinetics. This work unveils a versatile strategy to regulate the electronic structures of dual-metal sites with synergy by establishing charge transfer mechanism for dual-metal cocatalysts.

Cholinium Pyridinolate Ionic Pair-Catalyzed Fixation of CO2 into Cyclic Carbonates.

A halide-free ionic pair organocatalyst was proposed for the cycloaddition of CO2 into epoxide reactions. Cholinium pyridinolate ionic pairs with three different substitution positions were designed. Under conditions of temperature of 120 °C, pressure of 1 MPa CO2, and catalyst loading of 5 mol %, the optimal catalyst cholinium 4-pyridinolate ([Ch]+[4-OP]-) was employed. After a reaction time of 12 h, styrene oxide was successfully converted into the corresponding cyclic carbonate, and its selectivity was improved to 90%. A series of terminal epoxides were converted into cyclic carbonates within 12 h, with yields ranging from 80 to 99%. The proposed mechanism was verified by 1H NMR and 13C NMR titrations. Cholinium cations act as a hydrogen bond donor to activate epoxides, and pyridinolate anions combine with carbon dioxide to form intermediate carbonate anions that attack epoxides as nucleophiles and lead to ring opening. In summary, a halide-free ionic pair organocatalyst was designed and the catalytic mechanism in the cycloaddition of CO2 into epoxides reactions was proposed.

Aminocyclopropenium as a novel hydrogen bonding organocatalyst for cycloaddition of carbon disulfide and epoxide to prepare cyclic dithiocarbonate.

The smallest Hückel aromatic ring cyclopropenium substituted by electron-donating C-amino groups produced a aminocyclopropenium electron-rich cation. A bifunctional aminocyclopropenium halide catalyst installed with bis-(hydroxyethyl) functions on the amino group was then designed. A typical (diethanolamino)cyclopropenium halide catalyst C5·I was screened optimally for the cycloaddition of carbon disulfide into an epoxide to produce cyclic dithiocarbonate with an excellent conversion (95%) and high selectivity (92%). The electrostatic enhancement of alkyl C-H HBD capability was implemented via vicinal positive charges on the cyclopropenium core, and the acidity of the terminal O-H hydrogen proton increased by intramolecular H-bonding between the two hydroxy groups on the diethanolamino group (O-H⋯O-H). Then, a hybrid H-bond donor comprising enhanced alkyl C-H and hydroxy O-H was formed. The hybrid HBD offered by aminocyclopropenium was vital in activating the epoxide and stabilizing the intermediate, resulting in reduced O/S scrambling. Moreover, weakly coordinated iodide anion served as a nucleophilic reagent to open the ring of the epoxide. The cooperative catalytic mechanism of the HBD cation and halide anion was supported by NMR titrations and control experiments. Eleven epoxides with various substituents were converted into the corresponding cyclic thiocarbonate with high conversion and selectivity under mild conditions (25 °C, 6 h) without a solvent. The cycloaddition of carbon disulfide with epoxides catalyzed by aminocyclopropenium developed a new working model for hydrogen bonding organocatalysis.