Effect of Magnetite Particles on Photoinduced and Nonphotoinduced Free Radical Processes in Human Erythrocytes

Magnetite (Fe₃0₄) encapsulated in polystyrene microspheres dramatically decreased the time for 50% hemolysis (t_1/2) of human erythrocytes irradiated (λ300 nm) in the presence of ketoprofen (0.1 mM). The magnetic microspheres were present at a very low concentration (0.002%) such that on average there was only one particle per four erythrocytes. No such effect was seen when nonmagnetic microspheres were employed or when the equivalent concentration of soluble iron (FeCl₃) was present. A decrease in t_1/2 was also observed when the magnetic microspheres were added after UVA/ketoprofen treatment or when they were present during hemolysis initiated by thermolysis of 2,2′-azobis(2-amidinopro-pane). These findings may be attributed to an increase in the membrane concentration of lipid radicals as a result of a magnetic field-induced increase in radicals escaping from triplet radical pairs.     

均匀球状Fe3O4胶体粒子的制备

近年来,有关均匀胶体粒子的制备及其性质的理论研究已经成为一项新兴的研究领域.Fe_3O_4均匀胶体在催化剂、磁性材料、药物等方面具有广泛的用途,尤其值得注意的是其形成过程与钢铁的腐蚀过程极为相似,因此对Fe_3O_4均匀胶体的制备研究还将有助于钢铁腐蚀机理的阐明。Sugimoto和Matrijevic最初将Fe(OH)_2溶胶用氧化剂部分氧化而得到Fe_3O_4均匀胶体,但制备条件苛刻,操作复杂,且为了减小反应容器的大小对升温速率的影响,每次反应液的量只有10ml左右,一次制得的Fe_3O_4均匀胶体量只有约0.02克.本文报导在无防尘设备的简化实验条件下,通过在加液方法、除氧操作以及分离纯化等实验手续的修改后,对Fe_3O_4均匀粒子较大量制作所得到的结果。     

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.     

Effect of Supramolecular Inclusion on the 1,2‐Rearrangement of Free Radicals

The free radicals 3‐ethoxy‐2‐(ethoxycarbonyl)‐3‐oxopropyl ( 1 ^.) and 3‐ethoxy‐2‐(ethoxycarbonyl)‐2‐methyl‐3‐oxopropyl ( 2 ^.) were generated by photolysis of perester precursors in i) hexane solution, ii) in the presence of β‐cyclodextrin, and iii) in NaY zeolite. While free radicals in solution are reluctant to rearrange, they do so when encapsulated in β‐cyclodextrin or NaY zeolite. The coenzyme‐B₁₂‐dependent enzymic rearrangement of methylmalonyl‐CoA to succinyl‐CoA could be mimicked by photochemical generation of an analogue of the putative intermediate radical in a molecular container.     

Scavenging Effect of Perylenequinone Hydroxyls on Free Radicals: A Theoretical Study

Perylenequinonoidderivatives(PoD),includinghypocrellins,cercosporinandhypericin,etc.,arewidespreadnaturalphotosensitizers.Owingtoexcellentphotodynandcproperties,PoDhaveattractedmoreandmoreattention14.NowthemechanismsofthephotosensitizationofPoDhavebeenstudiedthoroughly,andclassicaltype1andtype11reactionsarefoundtobeinvolvedintheprocess'-':TherearemanyproblemstobesolvedbeforeusingPoDasaphotodynandcmedicine.Forexample,ithasnotbeensufficientlyunderstoodwhethertheactiveoxygens(O2,'O,)generated…     

Recombination of Photogenerated Lophyl Radicals in Imidazolium‐Based Ionic Liquids

Laser flash photolysis is applied to study the recombination reaction of lophyl radicals in ionic liquids in comparison with dimethylsulfoxide as an example of a traditional organic solvent. The latter exhibits a similar micropolarity as the ionic liquids. The ionic liquids investigated are 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ( 1 ), 1‐hexyl‐3‐methylimidazolium hexafluorophosphate ( 2 ), and 1‐butyl‐3‐methylimidazolium tetafluoroborate ( 3 ). The recombination of the photolytic generated lophyl radicals occur significantly faster in the ionic liquids than expected from their macroscopic viscosities and is a specific effect of these ionic liquids. On the other hand, this reaction can be compared with the macroscopic viscosity in the case of dimethylsulfoxide. Activation parameters obtained for lophyl radical recombination suggest different, anion‐dependent mechanistic effects. Quantum chemical calculations based on density functional theory provide a deeper insight of the molecular properties of the lophyl radical and its precursor. Thus, excitation energies, spin densities, molar volumes, and partial charges are calculated. Calculations show a spread of spin density over the three carbon atoms of the imidazolyl moiety, while only low spin density is calculated for the nitrogens.     

A Pulse Radiolysis Study of the Dynamics of Ascorbic Acid Free Radicals within a Liposomal Environment

The dynamics of free‐radical species in a model cellular system are examined by measuring the formation and decay of ascorbate radicals within a liposome with pulse radiolysis techniques. Upon pulse radiolysis of an N₂O‐saturated aqueous solution containing ascorbate‐loaded liposome vesicles, ascorbate radicals are formed by the reaction of OH^. radicals with ascorbate in unilamellar vesicles exclusively, irrespective of the presence of vesicle lipids. The radicals are found to decay rapidly compared with the decay kinetics in an aqueous solution. The distinct radical reaction kinetics in the vesicles and in bulk solution are characterized, and the kinetic data are analyzed.     

Advances in the Interfacial Assembly of Mesoporous Silica on Magnetite Particles

Interfacing magnetic particles with ordered mesoporous materials is an effective direction for the development of functional porous composite materials with rationally designed core–shell structures. Owing to the combined properties of magnetic nanoparticles and mesoporous silica (high surface area, large pore volume, porosity, and biocompatibility), core–shell magnetic mesoporous silica materials have generated tremendous interest in various disciplines, including chemistry, materials, bioengineering, and biomedicine. Interfacial assembly strategies enable the rational construction of magnetic mesoporous silica materials with well‐defined core–shell structure, morphology, pore parameters, and surface wettability, which can decisively influence their physical and chemical properties and thus improve their application performance. This Minireview summarizes recent progress in the synthesis of core–shell magnetic mesoporous silica and the adjustment of key parameters, including pore size, morphology, and pore orientation.     

苯酚类化合物在超微粒表面光解自由基的研究

研究了苯酚及其衍生物在超细微粒二氧化钛表面的光诱导电子转移和光化学反应过程，结果表明，在碱性条件下，苯酚类化合物较易于光降解，所生成的主要自由基为氢原子和苯氧基，体系中的羟基来源于超氧负离子基，而并非经由氢氧根HO~-失去电子后转变为HO~·，文中对于光诱导电子转移及有关光反应机理进行了分析讨论。     

Reduction of 4,4′-Stilbenequinone and 4,4′-Diphenoquinone upon Reaction with Photogenerated Radicals

The properties of 3,3′,5,5′-tetra-tert-butyl-4,4′-stilbenequinone (StQ) were studied by photochemical means. Acetone, acetophenone or benzophenone was photolyzed in the presence of both StQ and a donor, such as alcohols or triethylamine. This initiated reaction of a ketyl radical with StQ to form a semiquinone radical and eventually induce a permanent bleaching due to conversion of StQ to 4,4′-dihydroxystilbene (StQH₂). The quantum yield of conversion of StQ to StQH₂ increases with the donor concentration. Similar effects were found for the ketone-sensitized radical-induced conversions of the analogous diphenoquinone to the reduction product, diphenol.     

自由基检测技术进展

重点对主要的几种自由基检测技术的发展情况进行了讨论,并评价了各种方法的优缺点。涉及的自由基检测技术主要有分光光度吸收法与荧光方法、高效液相色谱法、化学发光法、电化学方法、自旋捕集技术和毛细管电泳方法,按间接检测方法和直接检测方法分类进行了评价。     

Magneto-Optical Properties of Silica Gel Containing Magnetite Fine Particles

The magnetic composite materials that consist of transparent matrix and magnetic fine particles are expected to have large residual magnetization and coercive force because of their fine magnetic domain structure, and also to show magneto-optical effects. Silica gels containing magnetite (Fe₃O₄) fine particles were prepared by sol-gel method. The magnetic, optical and magneto-optical properties of the composites were investigated by measurements of magnetization curves, UV-visible spectra and Faraday rotation in visible range. The saturation magnetization of the composite was almost as same as that expected from the amount of magnetite fine particles in it. Although the composites had large and broad absorption at around 400 nm, they still maintained their transparency. The origins of decrement of transparency attributed to the optical absorption of magnetite and scattering due to magnetite fine particles. The whole composites showed positive Faraday rotation under external static magnetic field due to the large contribution of diamagnetic silica gel matrix. Magnetite contributed negative Faraday rotation with maximum at around 470–480 nm to the magneto-optical spectra of the composites.     

Effect of Oxygen Free Radicals on Myosin in Muscle Fibres. A DSC and EPR study

Differential scanning calorimetry (DSC) and electron paramagnetic resonance spectroscopy (EPR, both conventional and saturation transfer EPR) were used to study the motional dynamics and segmental flexibility of myosin in muscle fibres in the presence of free radical generating system. Muscle fibre bundles isolated from psoas muscle of rabbit were spin-labelled with maleimide- and isothiocyanate-based probe molecules at the reactive sulfhydryl sites (Cys-707) of the motor domain. In the presence of hydroxyl free radicals the spectral intensity of the maleimide probe molecules decreased with time following a single exponential curve. MgADP and MgATP plus orthovanadate that produce flexibility changes in the multisubunit structure of myosin enhanced the reduction of the attached nitroxide molecules in free radical generating system. The analysis of the EPR spectra of spin-labelled and oriented fibres showed that the narrow distribution of spin labels changed in the presence of hydroxyl free radicals. Spectrum analysis by computer subtraction showed that short irradiation by UV light resulted in the enhancement of the ordered population at the expense of the disordered population. This suggests a transition of myosin heads from weak- binding state into strong-binding state. DSC measurements performed on calf cardiac myosin resulted in two main transitions at 49.4 and 54.1°C, respectively. Addition of MgADP produced a decrease of the 49.4°C transition, whereas a shift towards higher temperature was detected at the 54.1°C transition. It shows that there is an inter-site communication between the domains of the myosin. Hydroxyl free radicals induced further shifts of the transition temperatures and affected the width of the heat absorption curves. This revised version was published online in July 2006 with corrections to the Cover Date.     

Radicals Are Required for Thiol Etching of Gold Particles

Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process.     

On the Performance of Free Radicals Combined Electrocoagulation Treatment Processes

The electrocoagulation (EC) combined treatment processes have shown promising performances in which the removal of pollutants from industrial wastewater was greatly enhanced. The integration of a free radical producing step with EC has been considered as one of these new combinations that show synergy and improvements in the overall cleaning process performance. This review is devoted to discuss and analyze references on free radicals-assisted EC processes. Different combinations of free radical mechanisms were cited in the literature during the last two decades. They included ozone, advanced oxidation and ultrasound energy-assisted EC. It was noted that most of those studies were lab-scale processes that used synthetic wastewaters rather than real wastewaters. In addition the performances of those combined processes were improved compared to the EC process alone. This review considers the main parameters of free radical EC processes such as mechanisms, kinetic models, scale-up and cost estimation. Many concluding remarks were stated to give insights for possible future investigations. It seems from the results that the ozone-assisted EC is the most efficient combination since its removal efficiency is high in most applications. On the other hand, the combination of ultrasonic energy with EC was reported to reduce electrode passivation.     

稳定自由基掺杂有机物的动态核极化研究

The DNP-enhanced NMR experiment was performed on the DBF samples doped with free radicals. The experimental results show that it becomes very easy to perform the complicate NMR experiments under DNP enhancement. For the sample whose spin lattice relaxation is very slow, if it is doped with appropriate quantity free radicals.     

典型无机含氧酸自由基的特性

碳酸自由基、硝酸自由基、磷酸自由基和硫酸自由基是化学反应的重要中间体，都具有氧化性，对污染物在自然和人为环境中的迁移转化会产生重要的影响.文中较为详细地介绍这几种自由基的电极电位、产生方式、检测方法及与有机物的反应方式.总结四种自由基的特性及与有机物的反应方式可发现，四种自由基和羟自由基电极电位不同，导致它们和有机物反应速率的不同；碳酸自由基并不是羟自由基去除剂，对于一些容易被氧化的化合物，碳酸自由基氧化效果比羟自由基好；四种自由基均可由羟自由基转化而来，并且这四种自由基和羟自由基与有机物反应方式基本一致，都通过电子转移、夺氢和加成的方式进行.可以预测四种自由基和羟自由基降解有机物的机理将非常相似，今后应研究四种自由基与羟自由基相互转化的规律，以及与代表性有机物的反应机理.