{Ru(C6 H6 )}-Decorating Heteropolymolybdate for Highly Activity Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde.

An unclassical structure of {Ru(C6 H6 )}-based polyoxometalate, Cs6 H4 [Te2 Mo12 O46 {Ru(C6 H6 )}] ⋅ 16.5H2 O (1), has been successfully constructed from {Te2 Mo12 O46 }-type heteropolymolybdate and {Ru(C6 H6 )} group, which structure type was discovered for the first time. Compound 1 not only possesses strong light-harvesting ability, but also exhibits high carrier separation efficiency and lower charge transfer resistance. Under visible light irradiation, compound 1 displayed excellent catalytic activity and circularity in the conversion of benzyl alcohol to benzaldehyde (yield=94 %; turnover number=500; turnover frequency=20.8 h-1 ). Finally, the electron paramagnetic resonance measurement and energy level matching analysis provide theoretical basis for the derivation of the reaction mechanism.

Photocatalytic Reduction of Nitrobenzene to Aniline by an Intriguing {Ru(C6H6)}-Based Heteropolytungstate.

In this paper, we have successfully synthesized a structurally novel heteropolytungstate via coordination of four {Ru(C6H6)} and trivacant {TeW9O33} clusters, formulated as Cs4Na2H2[Te2W20O72(H2O){(C6H6)Ru}4]·12H2O (1). Compound 1 inherited the strong absorption of [Ru(C6H6)Cl2]2 in the visible region and {TeW9O33} in the UV region, providing a good basis for photocatalysis. As expected, compound 1 showed good photocatalytic activity in the visible-light-driven reduction of nitrobenzene using N2H4·H2O as a reductant with a yield of 99.8%, a high turnover number (TON = 330), and a high turnover frequency (TOF = 24 h-1). The cyclic experiment of nitrobenzene reduction indicated that compound 1 was an effective and stable heterogeneous catalyst. Finally, the nitrobenzene reduction pathway was affirmed using condensation with azobenzene as a reaction intermediate based on control experiments.

Construction of Hexameric Ru-Substitution POMs to Improve Photocatalytic H2 Evolution.

Converting solar energy into storable hydrogen energy by employing green photocatalytic technology offers a reliable alternative for meeting the energy crisis. The polyoxometalates are a promising candidate for hydrogen production photocatalysts because of their unique electronic and structural properties and controllable design at the molecular level. Introducing noble metals was proven to be an effective method to greatly enhance the photocatalytic efficiency of polyoxometalates. Herein, two unprecedented compounds of hexameric Ru-POMs, Na4H10[As2RuIV2W11O18(OH)4(H2O)6{AsW8RuIVO31(OH)Cl}2(B-ß-AsW9O33)4]·93H2O (1) and Na2H19[AsRuIII2W11O20(OH)2(H2O)6(RuIIICl3)(B-ß-AsW9O33)6]·90H2O (2), were successfully self-assembled. The H2 evolution rates of 1 and 2 under optimal conditions were 3578.75 and 3027.69 µmol h-1 g-1 with TONs of 255 and 205, respectively. The stability of 1 was demonstrated by a series of characterizations. Besides, a possible photocatalytic mechanism was proposed.

Numerical Analysis of Droplet Impact on the Convex Surface with Liquid Film.

Droplet impact on film is a common natural appearance in industrial production. The numerical simulation method is used to simulate the evolution process of droplet impact on different convex surfaces with liquid film to study the influence of various surface structures on the impact of droplets on the film. The mechanism of droplet impact on irregular wall is also explored. The effect of the height and width of the convex on the evolution of the interphase interface and the characteristic parameters of the crown and cavity are discussed. Based on the results, the convex has a great effect on the change form of droplets after impacting the liquid film. A region of high pressure will appear above the convex, and vortices will form around it. In terms of the characteristics of the crown, the growth rate of the crown height increases with the height of the convex. The spreading diameter of the crown increases with the height of the convex. The effect of convex width on the crown is less than that of convex height. The convex has a great influence on the evolution of the cavity, and the convex of different scales will affect the development shape of the cavity. The present finding provides theoretical guidance for the application of droplets impinging on liquid film.

Controlled Assembly of Ru-Containing Polyoxometalates for Photocatalytic Activity of the Primary Amine Coupling Reaction.

Three Ru-induced structural interconversion polyoxometalates (POMs), Na13H5[Ru4(H2O)2(Cl)2(WO2)4(AsW9O33)4]·43H2O (1), K5Na9H8[Ru2(WO2)4(AsW9O33)4]·50H2O (2), and KNa13H14[(WO2)4(AsW9O33)4]·34H2O (3), were successfully synthesized and thoroughly characterized. Interconversion of structures was accomplished by changing the number of active sites for compounds 1-3. All three compounds contain one {As4W40O140} unit, showing similar structural characteristics except for the active center number (Ru). Interestingly, compound 1 [turnover number (TON)= 486; turnover frequency (TOF)= 20 h-1] showed highly efficient photocatalysis in achieving oxidative coupling of primary amines. Compound 2 (TON = 406, TOF = 17 h-1) was also found to promote the oxidative coupling with relatively poor efficiency; however, compound 3 (TON = 178; TOF = 7.4 h-1) had no obvious contribution to the coupling reaction system, and a chain of evidence indicates that the catalytic performances are strongly dependent on element contents of active sites. Furthermore, the Ru-containing POM-based photocatalysts are conveniently recyclable and reusable during the photocatalytic processes. This study demonstrates the possibility of tuning the catalytic efficiency and stability of POM-based photocatalysts by well designing and controlling their structures. The possible reaction mechanism for the photocatalysis synthesis of imine product is also proposed based on experimental studies.

The Advances in Epigenetics for Cancer Radiotherapy.

Cancer is an important factor threatening human life and health; in recent years, its morbidity and mortality remain high and demosntrate an upward trend. It is of great significance to study its pathogenesis and targeted therapy. As the complex mechanisms of epigenetic modification has been increasingly discovered, they are more closely related to the occurrence and development of cancer. As a reversible response, epigenetic modification is of great significance for the improvement of classical therapeutic measures and the discovery of new therapeutic targets. It has become a research focusto explore the multi-level mechanisms of RNA, DNA, chromatin and proteins. As an important means of cancer treatment, radiotherapy has made great progress in technology, methods, means and targeted sensitization after years of rapid development, and even research on radiotherapy based on epigenetic modification is rampant. A series of epigenetic effects of radiation on DNA methylation, histone modification, chromosome remodeling, RNA modification and non-coding RNA during radiotherapy affects the therapeutic effects and prognosis. Starting from the epigenetic mechanism of tumorigenesis, this paper reviews the latest progress in the mechanism of interaction between epigenetic modification and cancer radiotherapy and briefly introduces the main types, mechanisms and applications of epigenetic modifiers used for radiotherapy sensitization in order to explore a more individual and dynamic approach of cancer treatment based on epigenetic mechanism. This study strives to make a modest contribution to the progress of human disease research.

"All-in-one" metal polyphenol network nanocapsules integrated microneedle patches for lipophagy fueled ferroptosis-mediated multimodal therapy.

Ferroptosis-mediated multimodal therapy has emerged as a promising strategy for tumor elimination, with lipid peroxide (LPO) playing a pivotal role. However, the therapeutic efficiency is limited due to insufficient intracellular levels of free fatty acids (FFA), which severely hinder the production of LPO. To address this limitation, we proposed a lipophagy strategy aimed at degrading lipid droplets (LDs) to release FFA, serving as the essential "fuel" for LPO production. In this study, the lipophagy inducer epigallocatechin gallate (EGCG) was self-assembled with reactive oxygen species (ROS)-producer phenethyl isothiocyanate (PEITC) mediated by Fe2+ to form EFP nanocapsules, which were further integrated into microneedle patches to form a "all-in-one" EFP@MNs. The metal-polyphenol network structure of EFP endow it with photothermal therapy capacity. Upon insertion into tumors, the released EFP nanocapsules were demonstrated to induce lipophagy through metabolic disturbance, thereby promoting LPO production and facilitating ferroptosis. When combined with photothermal therapy, this approach significantly remolded the tumor immune microenvironment by driving tumor-associated macrophages toward M1 phenotype and enhancing dendritic cell maturation. Encouragingly, in conjunction with αPD-L1 treatment, the proposed EFP@MNs exhibited remarkable efficacy in tumor ablation. Our study presents a versatile framework for utilizing microneedle patches to power ferroptosis-mediated multimodal therapy.

MDU-Net: multi-scale densely connected U-Net for biomedical image segmentation.

Biomedical image segmentation plays a central role in quantitative analysis, clinical diagnosis, and medical intervention. In the light of the fully convolutional networks (FCN) and U-Net, deep convolutional networks (DNNs) have made significant contributions to biomedical image segmentation applications. In this paper, we propose three different multi-scale dense connections (MDC) for the encoder, the decoder of U-shaped architectures, and across them. Based on three dense connections, we propose a multi-scale densely connected U-Net (MDU-Net) for biomedical image segmentation. MDU-Net directly fuses the neighboring feature maps with different scales from both higher layers and lower layers to strengthen feature propagation in the current layer. Multi-scale dense connections, which contain shorter connections between layers close to the input and output, also make a much deeper U-Net possible. Besides, we introduce quantization to alleviate the potential overfitting in dense connections, and further improve the segmentation performance. We evaluate our proposed model on the MICCAI 2015 Gland Segmentation (GlaS) dataset. The three MDC improve U-Net performance by up to 1.8% on test A and 3.5% on test B in the MICCAI Gland dataset. Meanwhile, the MDU-Net with quantization obviously improves the segmentation performance of original U-Net.

A heteropolytungstate based 2D layered porous framework with high proton conductivity.

A heteropolytungstate cluster [{Ru2O(bpy)2}2{Bi2W32O110}]10- (bpy = C10H8N2) was incorporated into a 2 : 1 type layered porous framework by interweaving the Na+ bridged cluster chains through the hydrogen bonding ability of the bpy ligands. It features multiple pore channels rich in hydrogen-bond network, contributing high conductivities > 10-2 S cm-1 at 298-358 K and 85% RH.

Polymyxin B sulfate inhalable microparticles with high-lectin-affinity sugar carriers for efficient treatment of biofilm-associated pulmonary infections.

Pulmonary infections caused by multidrug-resistant bacteria have become a significant threat to human health. Bacterial biofilms exacerbate the persistence and recurrence of pulmonary infections, hindering the accessibility and effectiveness of antibiotics. In this study, a dry powder inhalation (DPI) consisting of polymyxin B sulfate (PMBS) inhalable microparticles and high-lectin-affinity (HLA) sugar (i.e., raffinose) carriers was developed for treating pulmonary infections and targeting bacterial lectins essential for biofilm growth. The formulated PMBS-HLA DPIs exhibited particle sizes of approximately 3 µm, and surface roughness varied according to the drug-to-carrier ratio. Formulation F5 (PMBS: raffinose = 10:90) demonstrated the highest fine particle fraction (FPF) value (64.86%), signifying its substantially enhanced aerosol performance, potentially attributable to moderate roughness and smallest mass median aerodynamic particle size. The efficacy of PMBS-HLA DPIs in inhibiting biofilm formation and eradicating mature biofilms was significantly improved with the addition of raffinose, suggesting the effectiveness of lectin-binding strategy for combating bacterial biofilm-associated infections. In rat models with acute and chronic pulmonary infections, F5 demonstrated superior bacterial killing and amelioration of inflammatory responses compared to spray-dried PMBS (F0). In conclusion, our HLA carrier-based formulation presents considerable potential for the efficient treatment of multidrug-resistant bacterial biofilm-associated pulmonary infections.

Catalytic Enhancement of Cyclohexene Hydration by Ga-Doped ZSM-5 Zeolites.

Ga-doped ZSM-5 zeolites were directly synthesized by a facile one-step hydrothermal method without organic templates and calcination and then investigated in the cyclohexene hydration reaction. The structure, component, textural properties, and acidity of the as-prepared samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray fluorescence (XRF), Brunauer-Emmett-Teller (BET), ammonia temperature-programmed desorption (NH3-TPD), pyridine-chemisorbed IR (Py-IR), and 71Ga, 27Al, 29Si, and 1H magic-angle spinning (MAS) NMR techniques. The characterization results showed that the introduction of Ga atoms into the ZSM-5 zeolite framework is much easier than Al atoms and beneficial to promote the formation of small-sized crystals. The number of Brønsted acid sites of Ga-doped ZSM-5 samples obviously increased compared with Ga0-ZSM-5. Additionally, the highest cyclohexanol yield (10.1%) was achieved over the Ga3-ZSM-5 sample, while the cyclohexanol yield of the Ga0-ZSM-5 sample was 8.6%. This result indicated that the improved catalytic performance is related to its larger external surface area, smaller particle size, and more Brønsted acid sites derived from Si-OH-Al and Si-OH-Ga of Ga3-ZSM-5. Notably, the green route reduces harmful gas emission and provides a basis for doping other heteroatoms to regulate the catalytic performance of zeolites, especially in industrial production.

Experimental and numerical investigation of TVOC concentrations and ventilation dilution in enclosed train cabin.

Air pollution in trains is an important factor threatening human health, which has attracted more and more attention in the worldwide public health researches. In this study, one cabin of a fully enclosed train was taken as an example to conduct experimental and numerical research on pollution level and distribution characteristic of total volatile organic compound (TVOC). The results show that when the average emission rate under daily environmental conditions was taken as the reference, TVOC concentration in the cabin exceeded the limit level of Chinese Indoor Air Quality Standard by more than 4 times. The obvious pollutants accumulative phenomenon could be found at bottoms and corners under the action of airflow. Setting air inlets at the roof of the train, mean age of air ranged from 30 s to 50 s in the breathing area. The concentration of pollutants was the lowest at 2.5-5 m from the center point of the cabin structure, and the ventilation efficiency was the highest. The introduction of clean fresh air could effectively eliminate pollutants. When the complete displacement ventilation rates were 51.4 h-1 and 28.6 h-1, the removal efficiency of pollutants was about 0.85 and 0.48 mg/m3 per minute, respectively. This study was helpful to the improvement and optimization design of air quality and ventilation mode in trains.

An intriguing tetranuclear Rh-based polyoxometalate for the reduction of nitroarene and oxidation of aniline.

An organic-inorganic hybrid polyoxometalate Na5H5.68 [Na0.17Rh0.83III(C6H8N2)2Cl2]2(C8H8N2)2[As4W40O140Rh4IV(C6H4N2S)2]·nH2O (1) containing 5.66 Rh atoms is prepared; to our knowledge, it owns the largest number of Rh atoms in the Rh-POM family. Compound 1 demonstrates good catalytic performance in the reduction of nitrobenzene to aniline and the oxidation of aniline to azobenzene under mild conditions. Moreover, catalyst 1 exhibits high activity, excellent stability and recyclability.

Computed tomography-guided iodine-125 radioactive seed implantation in small-cell lung cancer: A retrospective study.

Purpose: To explore the efficacy of computed tomography (CT)-guided iodine-125 (125I) radioactive seed implantation for the treatment of small-cell lung cancer (SCLC). Material and methods: A total of 12 SCLC patients were retrospectively enrolled. All patients underwent CT-guided 125I seed implantation therapy, and were followed up until death, the last visit time, or study end time. Primary endpoint was the overall response rate (ORR). Secondary endpoints were local control rate (LCR), progression-free survival (PFS), overall survival (OS), and safety. Results: All patients were successfully implanted with 125I radioactive seeds. The ORR at 2, 6, 12, and 24 months after implantation was 83.3%, 63.6%, 50%, and 40%, respectively; the LCR at 1 and 2 years were 75% (6/8) and 60% (3/5), respectively; the median PFS and OS were 8 and 12 months, respectively; and the OS rate at 6, 12, and 24 months after implantation was 91.67%, 66.67%, and 41.67%, respectively. No surgery-related deaths occurred. During the follow-up period, mild complications were observed in patients, including worsening cough, hemoptysis, and pneumothorax. Conclusions: CT-guided 125I seed implantation therapy is a safe and effective supplementary treatment for SCLC patients, who cannot tolerate radiotherapy.

Strategy of boundary discretization in numerical simulation of laser propagation in skin tissue with vascular lesions.

Understanding light propagation in skin tissues with complex blood vessels can help improve clinical efficacy in the laser treatment of cutaneous vascular lesions. The voxel-based Monte Carlo (VMC) algorithm with simple blood vessel geometry is commonly used in studying the law of light propagation in tissues. However, unavoidable errors are expected in VMC because of the zigzag polygonal interface. A tetrahedron-based Monte Carlo with extended boundary condition (TMCE) solver is developed to discretize complex tissue boundaries accurately. Tetrahedra are generated along the interface, resulting in a polyhedron approximation to match the real interface. A comparison between TMCE and VMC shows neglected differences in the overall distribution of energy deposition of different models, but poor adaptability of the curved tissue interface in VMC leads to a higher energy deposition error than TMCE in a mostly deposited region in blood vessels. Replacing the real blood vessel with a cylinder-shaped vessel shows an error lower than that caused by VMC. Statistical significance analysis of energy deposition by TMCE shows that mean curvature has stronger relationship with energy deposition than the Gaussian curvature, which indicates the importance of this geometric parameter in predicting photon behavior in vascular lesions.

Performance Analysis of the Technology of High-Temperature Boiler Feed Water to Recover the Waste Heat of Mid-Low-Temperature Flue Gas.

In coal-fired power plants, most of the working fluids used in a mid-low-temperature flue gas waste heat recovery system (FGWHRS) are low-temperature boiler supply air or condensate water in the flue gas condenser. This is prone to cause low-temperature corrosion, as the system temperature is lower than the acid dew point of the flue gas. In this study, an experimental apparatus was set up at the entrance of the desulfurization tower of a 330 MW unit in Xinjiang, China, which uses the technology of high-temperature boiler feed water (above 80 °C) to recover the waste heat of mid-low-temperature flue gas. The heat exchange performance of the mid-low-temperature FGWHRS was evaluated under different working conditions, and the optimal input parameters of the system for each considered working condition are given based on the analysis. It was found that the low-temperature corrosion in the system could be avoided using this technology. To eliminate low-temperature corrosion, the lowest temperature for the inlet water was predicted to be 69 °C in our study via curve fitting based on the experimental data. The results could provide a theoretical basis and engineering guidance for determining the best heat recovery strategy of mid-low-temperature FGWHRS.