光致活性氧淬灭方法检测生物抗氧化剂动力学模型分析

以TiO2纳米颗粒光催化反应为模型,研究了反应过程中的活性氧( ROS)产生以及活性氧淬灭的反应动力学模型。对苯二甲酸分子与体系中的光催化反应产生的OH·反应,生成具有荧光性质的2-羟基对苯二甲酸( lex=315 nm,lem=425 nm),因此对苯二甲酸作为氧化探针分子与体系中的生物抗氧化剂( AOs)分子竞争与ROS的反应,根据体系的荧光、反应时间以及AOs的浓度建立了AOs淬灭ROS的反应动力学模型。根据此模型推导AOs清除ROS的动力学常数,发现常见的生物抗氧化剂的抗氧化活性大小顺序为：硫辛酸、没食子酸、谷胱甘肽、尿酸、维生素C、维生素E、水溶性维生素E和胆红素。     

活性氧自由基生成及传输对g-C_3N_4上NO光催化去除的影响:原位红外光谱与计算模拟结合法（英文）

石墨相氮化碳(g-C_3N_4)具有独特的二维层状结构和合适的能带结构,因而在可见光催化领域广受关注.尤其是在可见光去除环境污染物领域,得到了较为充分的研究与应用.然而g-C_3N_4去除环境污机理的反应机理尚不明确.因此,本文采用理论计算与实验高度结合的研究方法,以光催化NO去除为例,深入阐述了光照下g-C_3N_4表面活性氧物种(ROS)的生成及转化过程,及其介导下的NO光催化氧化机理.X射线衍射结果表明,g-C_3N_4是三嗪环层内聚合后层层堆叠而成,并由红外光谱确定了其表面的官能团类型.该结构经扫描电镜和透射电镜得到了进一步的验证.采用光致激发谱和紫外可见漫反射光谱等实验表征与密度泛函理论计算结合的光电性质分析,我们发现,g-C_3N_4在可见光下具有一定的响应,这为其在光催化去除NO中奠定了基础.同时,其价带位置过高,无法自行产生氧化性较强的羟基自由基(.OH).电子自旋共振技术结果表明g-C_3N_4在光照下能捕获到·O_2~-和·OH两种活性自由基.采用反应路径计算发现,·OH是由·O_2~-在导带上逐步得到电子被还原而生成,其中的速率控制步骤是H_2O_2的解离.因此,促进O_2分子的吸附和活化和克服H_2O_2解离的反应活化能是产生·OH和提升g-C_3N_4光催化氧化活性的关键.采用原位红外光谱技术对g-C_3N_4上NO的氧化去除过程进行了表征,发现其主要中间产物为NO_2,主要终产物为NO_2~-和NO_3~-,采用反应路径计算对该反应过程进行了理论模拟,发现在·O_2~-介导下,最高反应活化能为0.66 eV,而在·OH介导下,该活化能降低至0.46 eV,表明·OH的氧化性要明显强于·O_2~-.总之,本文采用一种可行的、高度结合的实验与计算手段研究了g-C_3N_4上ROS的生成及转化过程及其对NO去除的反应历程,在原子尺度揭示了该反应的机理,加深了对ROS在光催化环境污染物降解过程中作用的理解.     

二氧化钛光催化产生超氧自由基的形态分布研究

超氧阴离子自由基(O·-2)是TiO2光催化反应过程中产生的重要活性氧物种.本研究使用硝基四氮唑蓝(NBT)作为超氧自由基捕获剂,将其与TiO2混合后光照,研究TiO2光反应过程中产生的总O·-2;然后采用连续流动-分光光度法,将TiO2光照后,再与NBT混合,研究TiO2光反应过程中表面吸附的O·-2.在此基础上,研究了3种不同晶相TiO2(锐钛矿、金红石、P25)光催化反应中生成的总O·-2和表面吸附的O·-2.结果表明,3种不同晶相TiO2的总O·-2生成量依次为P25>锐钛矿>金红石;而表面吸附的O·-2的生成量相差不大,锐钛矿表面吸附O·-2略高.不同于以往仅对光催化反应中总活性氧(ROS)检测,本研究同时还对吸附在颗粒物表面ROS的产生和分布进行研究,有助于加深光催化污染物降解和微生物消毒作用机制的认识和理解.     

甲基叔丁基醚光催化降解的反应历程

以自制的TiO2为催化剂,在间歇式光催化反应装置中考察了水中甲基叔丁基醚的光催化降解反应.结果表明,水中MTBE在TiO2催化剂、氧气和紫外光照射的条件下能被光催化转化成无毒产物并最终被矿化.MTBE光催化降解过程中产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮,尽管降解速率不同,它们也都能被光催化降解.通过对反应物、中间物及产物的追踪分析,认为MTBE的光催化降解首先是通过羟基化过程来进行,进而提出MTBE光催化降解的可能反应历程.     

ZnS-CdS/SiO_2复合效应对光吸收及光催化性能的影响

用等体积浸渍法制备了一系列ZnS-CdS/SiO2复合半导体硫化物,采用XRD、TPR、UV-vis DRS和连续流动光催化反应对半导体材料的表面结构、能带结构、光吸收性能以及光催化反应性能进行了研究.结果表明:ZnS和CdS在载体表面发生复合作用,形成了CdxZn1-xS复合物,这种复合作用与焙烧温度以及ZnS/CdS比例有关,当煅烧温度为450℃且ZnS/CdS=1时,复合作用最强;ZnS和CdS间的复合效应对半导体材料的能带结构、吸光性能以及光催化性能产生了影响.复合作用越强其光催化CO2和CH4反应性能越高.     

有机分子荧光探针成像检测线粒体内ROS的研究进展

线粒体是细胞的"能量工厂",它利用氧气进行氧化磷酸化产生三磷酸腺苷(ATP),为细胞及生命体提供能量.同时,伴随着呼吸链中电子的泄漏,多种活性氧物种(ROS)在线粒体内快速产生.线粒体ROS在维持氧化还原平衡、参与调控细胞的增殖、分化、凋亡等行为方面发挥重要作用.当ROS水平超过机体抗氧化防御能力时,会导致疾病的发生.因此,发展准确检测线粒体ROS的方法,对深入探究ROS的细胞功能调控及相关疾病的发生发展意义重大.由于ROS存在浓度低、寿命短、反应活性高等特点,对其进行精准检测是化学、生物学及医学领域的一大挑战.荧光成像技术具有时空分辨率高、生物相容性好、灵敏度高等显著优势,成为实时检测细胞及活体内ROS的有力工具.近年来,相继发展了诸多荧光探针,实现了线粒体ROS的成像分析.本文着重总结与评述了近年来发展靶向线粒体、荧光可视化多种ROS有机分子探针工作的研究进展,并在构建新型线粒体荧光探针、进一步利用荧光成像方法深入剖析线粒体ROS的细胞学功能等方面进行了探讨与展望.     

SERS纳米探针对电刺激过程中细胞内产生活性氧的检测

电刺激是用于细胞内紊乱电活动引起疾病的一类重要治疗方式. 在电刺激过程中是否会诱导细胞内活性氧(ROS)水平的改变, 以及常规抗氧化抑制药物与电刺激治疗同时运用带来的影响, 目前尚未有相关研究. 本文设计了一种具有较好生物相容性的金/银核壳纳米棒表面增强拉曼(SERS)活性探针, 用于电刺激过程中细胞内产生ROS的检测. 将该探针与细胞共孵育, 使其内化入细胞, 对细胞进行不同时间的电刺激, 利用拉曼光谱对SERS探针的信号进行检测. 实验结果表明, 随着电刺激时间的延长, SERS信号减弱, 说明细胞内产生ROS的量明显增加. 该传感机制是利用ROS能刻蚀金/银核壳纳米棒的银壳, 从而使其变薄引起SERS信号减弱. 抗坏血酸(AA)和谷胱甘肽(GSH)两种抗氧化抑制剂类药物与电刺激同时运用时, 可观察到它们会对电刺激过程产生的ROS有清除作用. 该研究发展了一类用于细胞内ROS检测的光谱方法, 也为异常的氧化应激和肿瘤治疗过程中的组合用药提供了建议.     

银在光催化分解NO反应中的光催化行为研究

以光催化分解NO反应为探针,研究了负载银催化剂在紫外光激发作用下光催化分解NO反应的催化行为.对银物种的调变会对银的光催化活性产生显著影响,结合XRD(X射线粉末衍射),UV-vis(紫外可见漫反射)等表征手段对反应中起重要作用的活性银物种的表征结果表明,高度分散于分子筛内的银离子及银簇是光催化分解NO的活性中心.     

TiO2和ZnO表面CO光催化氧化活性研究

在TiO2和ZnO表面CO光催化氧化研究中发现,365 nm紫外光照下TiO2表面无活性,而ZnO表面却有明显的CO光催化氧化活性.研究表明,主要是由于紫外光照下,ZnO光分解而TiO2没有光分解,从而在表面产生不同吸附形态的氧所致.而且,ZnO表面CO光催化氧化反应活性可在27 h内保持稳定,暗示气相光催化反应中,ZnO不会因为光腐蚀而使其催化活性降低.     

硫化镉光催化氧化二苯甲醇的反应

半导体粉能对烯烃, 芳烃等的光催化氧化, 但效率低, 揭示其机理, 研究提高催化效率是研究半导体光催化的突出问题. 本文研究了硫化镉粉末光催化氧化二苯甲醇的反应, 发现能从硫化镉导带上捕获电子的物质都能促使电荷分离, 引发或加速反应, 而自由基猝灭剂却能完全猝灭反应. 本文进一步揭示了硫化镉光催化特性并探讨了反应机理.     

Molecular‐Level Understanding of the Photocatalytic Activity Difference between Anatase and Rutile Nanoparticles

The generation of oxidants on illuminated photocatalysts and their participation in subsequent reactions are the main basis of the widely investigated photocatalytic processes for environmental remediation and selective oxidation. Here, the generation and the subsequent diffusion of ^.OH from the illuminated TiO₂ surface to the solution bulk were directly observed using a single‐molecule detection method and this molecular phenomenon could explain the different macroscopic behavior of anatase and rutile in photocatalysis. The mobile ^.OH is generated on anatase but not on rutile. Therefore, the photocatalytic oxidation on rutile is limited to adsorbed substrates whereas that on anatase is more facile and versatile owing to the presence of mobile ^.OH. The ability of anatase to generate mobile ^.OH is proposed as a previously unrecognized key factor that explains the common observations that anatase has higher activity than rutile for many photooxidative reactions.     

Photocatalytic Generation of N‐Centered Hydrazonyl Radicals: A Strategy for Hydroamination of β,γ‐Unsaturated Hydrazones

A visible‐light photocatalytic generation of N‐centered hydrazonyl radicals has been accomplished for the first time. This approach allows efficient intramolecular addition of hydrazonyl radical to terminal alkenes, thus providing hydroamination and oxyamination products in good yields. Importantly, the protocol involves deprotonation of an N? H bond and photocatalytic oxidation to an N‐centered radical, thus obviating the need to prepare photolabile amine precursors or the stoichiometric use of oxidizing reagents.     

Radical Addition Enables 1,2‐Aryl Migration from a Vinyl‐Substituted All‐Carbon Quaternary Center

An efficient method for photocatalytic perfluoroalkylation of vinyl‐substituted all‐carbon quaternary centers involving 1,2‐aryl migration has been developed. The rearrangement reactions use fac‐Ir(ppy)₃, visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all‐carbon quaternary center with the concomitant generation of a C‐radical bearing two electron‐withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.     

Photogenerated Neutral Nitrogen Radical Catalyzed Bifunctionalization of Alkenes

Alkene bifunctionalizations are powerful tools for the rapid construction of structurally complex and valuable scaffolds, and such reactions typically involve the use of transition-metal catalysts or organocatalysts. Here, we report for the first time a photogenerated neutral nitrogen radical catalyzed intermolecular alkene bifunctionalization by using allyl sulfones as the source of both the carbon and the sulfone functionalities under mild conditions. The key to the success of this protocol involves the visible-light-mediated photocatalytic in situ generation of a nitrogen-centered radical from the N-(2-acetylphenyl) benzenesulfonamide catalyst, and its activation of the allyl sulfones to generate reactive species. The preliminary control experiments supported the postulated mechanism.     

Recent Advances of Zinc-based Antimicrobial Materials

Zinc has been widely utilized as an antimicrobial material, often in the form of complexes or zinc oxide nanoparticles. The efficacy of zinc complexes are often due to the synergistic effect of both the zinc ions and the attached organic ligands. In contrast, the nanoparticle effect of ZnO, and the photocatalytic generation of reactive oxygen species (ROS) has been postulated to be the effective mechanism of ZnO as a biocide. Recently, new forms of zinc-based biocidal materials have been reported with distinct antimicrobial mechanisms. This minireview summarizes these recent advances, including zinc-based nano-arrays, MOF-based ROS release and zinc composites that can self-generate ROS.     

Phenols as Novel Photocatalytic Platforms for Organic Synthesis

In recent years, organic chemists have devoted a great deal of effort towards the implementation of novel green photocatalytic synthetic protocols. To this end, the development of new effective, non-toxic, inexpensive photocatalysts, which are capable of driving value-added chemical transformations, is highly desirable. Interestingly, phenols fulfill all these requirements due to their outstanding physicochemical features, therefore emerging as promising metal-free photocatalytic platforms for organic synthesis. This Perspective aims at highlighting the most recent applications of phenols in organic photocatalysis. More specifically, phenolate anions, formed upon deprotonation of phenols, are photo-active organic intermediates that may absorb light within the visible region. Thus, when in the excited states, these anions may be used as reductants to generate reactive open shell species from suitable precursors under mild operative conditions. Alternatively, phenolate anions and suitable radical precursors can form electron donor-acceptor (EDA) complexes. Specifically, the photochemical activity of these molecular aggregates can be used to initiate organic radical reactions. Lastly, forward-looking opportunities within this research field have been discussed.     

Polymer Dots Compartmentalized in Liposomes as a Photocatalyst for In Situ Hydrogen Therapy

Semiconducting polymer dots (Pdots) have recently attracted considerable attention because of their photocatalytic activity as well as tunable optical band gap. In this contribution, we describe the therapeutic application of Pdots through in situ photocatalytic hydrogen generation. Liposomes were employed as nanoreactors to confine the Pdot photocatalyst, reactants, intermediates, and by‐products. Upon photon absorption by the Pdots, the catalytic cycle is initiated and repeated within the aqueous interior, while the H₂ product diffuses across the lipid bilayer to counteract reactive oxygen species (ROS) overexpressed in diseased tissues. Ensemble and single‐particle Förster resonance energy transfer microscopy confirmed the proposed nanoreactor model. We demonstrate that a liposomal nanoreactor containing Pdots and a sacrificial electron donor is a potential photocatalytic nanoreactor for in situ hydrogen therapy.     

氢还原二氧化钛光催化降解磺基水杨酸的研究

研究了由偏钛酸在不同温度下焙烧制成的TiO2,经氢还原后用于光催化降解磺基水杨酸（SSal) 以及TiO2的漫反射光谱和荧光光谱特征。结果表明,锐钛型TiO2在经550℃ 氢还原处理120min后,光催化活性明显提高;600℃条件下焙烧制得的TiO2,经氢还原后其光催化降解SS al的反应活性最高。漫反射光谱结果表明,800℃条件下焙烧制得的TiO2,开始出现转晶现象,从锐钛型逐渐向金红石型过渡。TiO2荧光光谱的峰面积（F）和倍频峰面积（R）的比值越大。TiO2光催化降解SSal的活性越高,提出了氢还原后TiO2的光催化作用机制。