纳米零价铁活化分子氧原理及降解有机污染物性能增强策略

纳米零价铁直接还原降解有机污染物运行长效性差,且不能矿化有机污染物.利用纳米零价铁还原活化分子氧生成活性氧物种可以氧化甚至矿化有机污染物.在最近的研究中,作者提出了纳米零价铁活化分子氧的双途径机理,即铁核电子转移到氧化铁壳表面的双电子还原活化分子氧途径和氧化铁表面结合态亚铁离子的单电子还原活化分子氧途径,阐释了纳米零价铁核壳结构依赖的分子氧活化降解有机污染物性能机制及性能增强策略.证实在纳米零价铁活化分子氧体系添加少量亚铁离子能在零价铁表面形成更多的结合态亚铁,显著增强纳米铁表界面活性氧物种生成量;同时,在纳米零价铁活化分子氧体系中引入少量有机或无机配体亦可提高活性氧物种产生效率,从而增强有机污染物降解性能.最后讨论了典型环境因素如pH值、共存离子、天然有机物等影响纳米零价铁活化分子氧降解有机污染物性能的规律.     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

Renal Clearable Luminescent WSe2 for Radioprotection of Nontargeted Tissues during Radiotherapy

High‐energy ionizing radiation is widely used in medical diagnosis and cancer radiation therapy. However, high‐energy radiation can also impose significant damages in healthy tissues during medical treatments via direct DNA damages and indirect damages from production of reactive oxygen species (ROS). Therefore, it is urgent to develop highly effective radioprotectants with low toxicities that can meet the increasing needs for alleviating the adverse effects from cancer radiation therapy and nuclear emergency. In this work, strongly catalytic ultrasmall (sub‐5 nm) cysteine‐protected WSe₂ dots are employed to protect healthy tissues against radiation via diminishing radiation‐induced free radicals. The WSe₂ dots with high surface activities can recover radiation‐induced DNA damages and eliminate the excessive ROS generated from radiation. In vivo experiments confirm that the survival rate of mice treated with WSe₂ dots is significantly elevated with radiation damages postponed under exposure to high‐dose ionizing radiation. Furthermore, the free radicals in major organs and hematological system can be appreciably omitted, suggesting their unique role as free radical scavengers. These WSe₂ dots in ultrasmall size show rapid renal clearance of ≈74% injection dose via urine excretion in 24 h and do not cause any apparent toxicity in vivo for up to 30 d.     

光合释氧机理的ABEEM/MM/MD和BS-DFT理论研究

建立了S₂态光合释氧络合物（OEC）的原子-键电负性均衡模型（ABEEMσπ）的电荷参数,并使用ABEEM/MM/MD可极化力场的分子动力学模拟和对称性破损的DFT研究了光合作用制造氧气的微观机制.HF/STO-3G（采用此基组的原因请见引用文献）水平下的电荷拟合结果证明了ABEEMσπ模型计算电荷分布的合理性和高效性.MD模拟显示,S₂态Mn₄CaO₅的双向异构化过程伴随Ca上的水分子W3转移至Mn1（III）/Mn4（III）,它很可能作为底物水之一,与O5在S₄态结合产生O₂.基于此,考察了全自旋态下两种异构体形式中O－O键形成的自由基耦合机理.BS-DFT计算结果表明,开立方结构的释氧活性大大优于闭立方结构,金属锰和氧自由基的自旋耦合方式也是反应性的决定性因素,同时,OEC的结构灵活性对于S态循环和光合水分解至关重要.     

氧还原碳基非贵金属电催化剂研究进展

质子交换膜燃料电池是一种直接将化学能转化为电能的能量转换装置,具有环境友好、能量密度高、转化效率高等优点,能够应用于便携能源及燃料电池电动车领域.但燃料电池阴极氧还原需要大量的铂基催化剂,铂价格昂贵、储量有限、易中毒的缺点限制了它的实际应用.因此,开发低成本、高活性、高稳定性的阴极非贵金属催化剂将能够显著推动质子交换膜燃料电池的大规模商业化应用.其中碳基非贵金属催化剂作为最有可能替代铂的氧还原催化剂,引起了广泛的研究.基于此,本文首先简单介绍了氧还原的机理;其次将碳基非贵金属催化剂分为过渡金属氮碳催化剂和非金属掺杂碳催化剂,对它们在材料制备和活性中心的研究进行了总结和讨论;最后,报道了碳基非贵金属催化剂在质子交换膜燃料电池单电池中的应用进展.     

基于炉口火焰辐射测温的转炉终温预测研究

转炉炼钢的铁水终点温度是衡量铁水是否符合出钢要求的一个重要指标,目前仍主要依靠人工经验进行控制,其预测精度难以保证。为了能够有效的预测终点铁水的温度,并能满足不同的转炉炉口尺寸的要求,提出了一种基于炉口火焰温度测量的转炉终点铁水温度预测的新方法。利用可以采集可见光和近红外波段的微型光谱仪作为关键器件构建了炉口火焰辐射信息的采集系统,实现对转炉炼钢现场的炉口火焰辐射信息进行实时、有效的采集。同时综合考虑了炉口火焰的实际温度范围和现场的测量距离,通过改进的系统标定方法,对所构建的辐射信息采集系统进行标定,并利用双波长法获得了炉口火焰的辐射温度。鉴于炉口的火焰温度与炉内的铁水温度之间存在着一定的联系,还利用所测得的火焰温度以及与铁水温度相关的转炉吹炼过程参数,建立了基于支持向量机的炉内铁水温度的回归预测模型。对68炉现场采集到的转炉吹炼数据进行验证实验后表明该方法的预测精度要优于人工经验,且接近采用副枪的铁水温度测量方式,可为中小型转炉的终点温度预测提供一种有效可行的方案。     

二氧化氮溶于水定量实验的设计与研究

设计了NO2溶于水的定量实验。实验发现,把装满NO2的试管倒立于水中,待数分钟后试管内液面基本稳定,此时管内液体上升的体积远大于试管容积的2/3,若等待时间足够长(14 h),液体可充满整个试管。进一步研究表明,造成这种现象的可能原因,一方面与制取NO2时浓硝酸的饱和蒸气压有关,另一方面与NO自身溶于水并与水溶氧反应有关,还与NO能溶于稀硝酸有关,而与NO2的二聚无关。液体能充满整个试管可能应与氧气在水中的扩散有紧密关系。     

基于原理解读的铁吸氧腐蚀实验再设计

由教材中吸氧腐蚀原理的解读引发思考, 对相关铁吸氧腐蚀实验再研究, 从溶液中的氧气参与吸氧腐蚀反应的角度设计吸氧腐蚀实验器, 用数字化实验技术中的溶解氧传感器进行实验, 能直观形象地看到溶解氧参与反应, 且有电流产生, 还探究了氯化钠溶液进行实验时的最佳浓度。     

两步热化学分解水制氢用氧交换材料

氧交换材料是一种能够在惰性或还原气氛中快速释氧,而在弱氧化气氛下(如水蒸气)恢复氧的储氧材料。基于氧交换材料的太阳能热化学分解水制氢技术可实现太阳能向氢能的高效转化。该技术利用太阳能提供热量使氧交换材料高温释氧或被还原性气体还原,而后与水发生氧化反应生成纯氢。将氧交换材料制成透氧膜,在膜的两侧发生材料的释氧和氧恢复,同时实现纯氢的连续制备。本文详细论述了铁基氧化物、钙钛矿氧化物、镍基氧化物、铈基氧化物、无机透氧膜等氧交换材料的研究成果,重点介绍了基于不同反应体系氧交换材料的应用情况,并就提高铁基氧化物、钙钛矿氧化物等典型氧交换材料反应活性与循环稳定性的可能路径,构建高效透氧膜反应器的难点与发展方向等主要问题进行了探讨与展望。     

Neuroprotective Ability of Apocynin Loaded Nanoparticles (APO-NPs) as NADPH Oxidase (NOX)-Mediated ROS Modulator for Hydrogen Peroxide-Induced Oxidative Neuronal Injuries

Apocynin (APO) is a known multi-enzymatic complexed compound, employed as a viable NADPH oxidase (NOX) inhibitor, extensively used in both traditional and modern-day therapeutic strategies to combat neuronal disorders. However, its therapeutic efficacy is limited by lower solubility and lesser bioavailability; thus, a suitable nanocarrier system to overcome such limitations is needed. The present study is designed to fabricate APO-loaded polymeric nanoparticles (APO-NPs) to enhance its therapeutic efficacy and sustainability in the biological system. The optimized APO NPs in the study exhibited 103.6 ± 6.8 nm and −13.7 ± 0.43 mV of particle size and zeta potential, respectively, along with further confirmation by TEM. In addition, the antioxidant (AO) abilities quantified by DPPH and nitric oxide scavenging assays exhibited comparatively higher AO potential of APO-NPs than APO alone. An in-vitro release profile displayed a linear diffusion pattern of zero order kinetics for APO from the NPs, followed by its cytotoxicity evaluation on the PC12 cell line, which revealed minimal toxicity with higher cell viability, even after treatment with a stress inducer (H₂O₂). The stability of APO-NPs after six months showed minimal AO decline in comparison to APO only, indicating that the designed nano-formulation enhanced therapeutic efficacy for modulating NOX-mediated ROS generation.