An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

Influence of surfactants on rheological behaviors of polyacrylonitrile/dimethyl sulfoxide/silicon blending polymer solutions

KH550, KH560, CTAB, and F127 were adopted to modify silicon (Si) to improve the dispersity and stability of Si in the polyacrylonitrile/dimethyl sulfoxide (PAN/DMSO) polymer solutions. The influence of surfactants on rheological behaviors of PAN/DMSO/Si blending polymer solutions was investigated by an advanced solution and melt rotation rheometer. The homogeneity and stability were also studied. The results showed that the surfactants could change the viscosity dependence of blending polymer solutions on shear rate, temperature and storage time by increase the steric hindrance of Si. Among the four solutions, PAN/DMSO/Si blending polymer solution with F127 exhibited the lowest viscosity, activation energy and the smallest structural viscosity index and exhibited the trend close to the Newtonian fluids. Moreover, PAN/DMSO/Si blending polymer solution with F127 exhibited the best dispersity and stability, indicating its best physical properties and machinability.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Research and development of liquid hydrogen (LH2) temperature monitoring system for marine applications

Monitoring the temperature in liquid hydrogen (LH₂) storage tanks on ships is important for the safety of maritime navigation. In addition, accurate temperature measurement is also required for commercial transactions. Temperature and pressure define the density of liquid hydrogen, which is directly linked to trading interests. In this study, we developed and tested a liquid hydrogen temperature monitoring system that uses platinum resistance sensors with a nominal electrical resistance of approximately 1000 Ω at room temperature, PT-1000, for marine applications. The temperature measurements were carried out using a newly developed temperature monitoring system under different pressure conditions. The measured values are compared with a calibrated reference PT-1000 resistance thermometer. We confirm a measurement accuracy of ±50 mK in a pressure range of 0.1 MPa–0.5 MPa.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

药物相互作用研究在新药研发和审评决策中的应用

药物相互作用改变了剂量效应关系，可能会降低疗效或增加毒性，是临床应用中合并用药治疗时重要的考虑因素。预测具有临床意义的药物相互作用是药物研发过程中获益风险评估的重要环节。本文概述了药物研发过程中药物相互作用研究的目的和意义，体内和体外研究的主要内容；梳理分析了2020年国家药品监督管理局（National Medical Products Administration, NMPA）和美国食品药品监督管理局（Food and Drug Administration, FDA）批准上市的新药药物相互作用研究情况，旨在为我国药物研发过程中药物相互作用研究及其监管审评提供参考。     

Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

A comprehensive survey on computer vision based concepts,methodologies, analysis and applications for automatic gun/knife detection

The ability to detect gun and gun held in hand or other body parts is a typical human skill. The same problem presents an imperative task for computer vision system. Automatic observer independent detection of hand held gun or gun held in the other body part, whether it is visible or concealed, provides enhance security in vulnerable places and initiates appropriate action there. Compare to the automatic object detection systems, automatic detection of gun has very few successful attempts. In the present scope of this paper, we present an extensive survey on automatic detection of gun and define a taxonomy for this particular detection system. We also describe the inherent difficulties related with this problem. In this survey of published papers, we examine different approaches used in state-of-the-art attempts and compare performances of these approaches. Finally, this paper concludes pointing to the possible research gaps in related fields.