Photooxidation of nucleic acids on metal oxides: physico-chemical and astrobiological perspectives

Photocatalytic oxidation of nucleic acid components on aqueous metal oxides (TiO(2), α-FeOOH, and α-Fe(2)O(3)) has been studied. The oxidation of purine nucleotides results in the formation of the purine radical cations and sugar-phosphate radicals, whereas the oxidation of pyrimidine nucleotides other than thymine results in the oxidation of only the sugar-phosphate. The oxidation of the thymine (and to a far less extent for the 5-methylcytosine) derivatives results in deprotonation from the methyl group of the base. Some single stranded (ss) oligoribonucleotides and wild-type ss RNA were oxidized at purine sites. In contrast, double stranded (ds) oligoribonucleotides and DNA were not oxidized. These results account for observations suggesting that cellular ds DNA is not damaged by exposure to photoirradiated TiO(2) nanoparticles inserted into the cell, whereas ss RNA is extensively damaged. The astrobiological import of our observations is that the rapid degradation of monomer nucleotides make them poor targets as biosignatures, whereas duplex DNA is a better target as it is resilient to oxidative diagenesis. Another import of our studies is that ds DNA (as opposed to ss RNA) appears to be optimized to withstand oxidative stress both due to the advantageous polymer morphology and the subtle details of its radical chemistry. This peculiarity may account for the preference for DNA over RNA as a "molecule of life" provided that metal oxides served as the template for synthesis of polynucleotides, as suggested by Orgel and others.     

A kinetic study of ozone decomposition on illuminated oxide surfaces

The heterogeneous chemistry and photochemistry of ozone on oxide components of mineral dust aerosol, including α-Fe(2)O(3), TiO(2), and α-Al(2)O(3), at different relative humidities have been investigated using an environmental aerosol chamber. The rate and extent of ozone decomposition on these oxide surfaces are found to be a function of the nature of the surface as well as the presence of light and relative humidity. Under dark and dry conditions, only α-Fe(2)O(3) exhibits catalytic decomposition toward ozone, whereas the reactivity of TiO(2) and α-Al(2)O(3) is rapidly quenched upon ozone exposure. However, upon irradiation, TiO(2) is active toward O(3) decomposition and α-Al(2)O(3) remains inactive. In the presence of relative humidity, ozone decay on α-Fe(2)O(3) subject to irradiation or under dark conditions is found to decrease. In contrast, ozone decomposition is enhanced for irradiated TiO(2) as relative humidity initially increases but then begins to decrease at higher relative humidity levels. A kinetic model was used to obtain heterogeneous reaction rates for different homogeneous and heterogeneous reaction pathways taking place in the environmental aerosol chamber. The atmospheric implications of these results are discussed.     

α-Fe2O3形貌对Au/α-Fe2O3催化一氧化碳氧化反应性能的影响

负载型纳米金催化剂由于其独特的化学性质在一系列氧化反应中受到广泛关注.其中,一氧化碳氧化不仅在实际应用领域(如汽车尾气处理)发挥重要作用,而且作为一种理想的模型反应用以深入研究和理解催化剂的构效关系.为了获得高效的纳米金催化剂,我们需要把金负载到载体上,载体不仅为金的分散提供必要的表面,而且还会和金产生相互作用,这种金属-载体相互作用对金的氧化态,金颗粒大小及其热稳定性均有重要影响.金属氧化物是负载金最常用的载体.为了提高纳米金催化剂的性能,需要调变金属氧化物的性质.常用的策略是调控金属氧化物的组成、晶相以及晶粒大小.此外,对金属氧化物的形貌进行精细调控也是一种重要的方法,因为具有不同形貌的氧化物可能会暴露出不同的晶面,而且可能具有不同的缺陷位点.α-Fe₂O₃是一种热稳定性强而且对环境友好的载体,可是有关其形貌对负载金催化剂在一氧化碳氧化反应中性能影响的研究尚不充分.因此,本文采用水热法合成了具有纳米球和纳米棒两种形貌的氧化铁,并采用沉积-沉淀的方法将金纳米颗粒负载于其表面.高分辨透射电镜照片显示,和氧化铁纳米球(α-Fe₂O₃(S))相比,氧化铁纳米棒(α-Fe₂O₃(R))的表面更为粗糙,具有更多的缺陷位点.Au和α-Fe₂O₃(R)之间有更强的金属载体相互作用,导致纳米棒氧化铁上的金纳米颗粒更小而且多呈半球形.相比之下,纳米球氧化铁上的金纳米颗粒较大,多呈球形,且分布不均匀.反应结果表明,Au/α-Fe₂O₃(R)具有更高的一氧化碳氧化活性.对反应后的催化剂进行表征发现,Au/α-Fe₂O₃(R)上金颗粒烧结程度较低,平均粒径从1.5增至2.4 nm,而Au/α-Fe₂O₃(S)上金颗粒烧结较为严重,平均粒径从2.0 nm增加到4.0 nm.氢气程序升温还原结果表明,Au/α-Fe₂O₃(R)具有更强的还原性,这也促进了其催化活性的提高.     

纺锤形β-FeOOH纳米结构和α-氧化铁亚微米/微米粒子的合成与转变

使用一种简易的无表面活性剂辅助的水热合成方法,在温度为140 ℃时实现了纺锤形β-FeOOH纳米结构向α-氧化铁亚微米/微米粒子的转变。研究表明,通过实验参数的简单调控,实现了单晶α-氧化铁亚微米粒子与β-FeOOH的纺锤形纳米结构和纳米棒的控制制备。基于实验结果,提出了该过程中的相转变机理。     

氧化铁和羟基氧化铁光催化还原银离子

在波长λ≥320 nm的紫外灯照射下, 水溶液中的银离子能在氧化铁和羟基氧化铁催化剂表面发生还原反应而生成颗粒银. 在这些催化剂上, Ag(I)的等温吸附线都符合Langmuir吸附方程; Ag(I)的初始还原速率均随其初始吸附量的增加而线性增大, 并且增大的幅度依α-Fe2O3>α-FeOOH>γ-Fe2O3>γ-FeOOH>δ-FeOOH的顺序降低. 但是, 在前三种催化剂上, 只有当Ag(I)的吸附量达到其饱和吸附量的一半时, Ag(I)的还原才能发生, 并且几乎不受氮气的影响. 在δ-FeOOH和TiO2体系中通入氮气, 能显著加快Ag(I)的光催化还原. 这说明O2与Ag(I)竞争催化剂上的吸附位点和还原物种, 且与催化剂的性质有关. XRD分析表明, α-Fe2O3和δ-FeOOH分别具有较好和较差的结晶度. 这说明氧化铁和羟基氧化铁的结晶度越高, 越有利于光生载流子的分离及其与表面目标物种发生氧化还原反应.     

葡聚糖分子对氢氧化铁矿化结晶的调制作用

通过对比五种不同葡聚糖浓度的Fe3＋/葡聚糖矿化作用体系中Fe(OH)3凝胶在早期矿化阶段的成核和相变过程来研究葡聚糖对铁矿物的结晶与转化的调控作用. 运用ICP-AES(等离子发射光谱仪)观察各个矿化体系中上清液的[Fe3＋]浓度及相应pH的变化, 矿化产物运用FTIR、XRD进行表征. 结果发现, 上清液中[Fe3＋]经历了两次下降过程, 在陈化的第三天突然回增. 与不含葡聚糖的矿化作用体系很快形成结晶良好的α-FeOOH不同, 在含有葡聚糖的矿化作用体系中最初形成的物相主要为β-FeOOH. 葡聚糖分子通过与Fe3＋配位吸附在铁氧化物颗粒的表面促进了β-FeOOH转化为α-Fe2O3. 相变是经过溶解-再结晶机制进行的. [Fe3＋]第二次下降正是由于β-FeOOH转化为α-Fe2O3引起的. 葡聚糖浓度适当增大, β-FeOOH溶解加快, 有利于相变的进行. 因此葡聚糖的存在能显著影响在氢氧化铁凝胶中形成晶核的结构类型及其相变历程.     

Reaction products and kinetics of the reaction of NO2 with γ-Fe2O3

The reaction of NO(2) with Fe(2)O(3) has relevance for both atmospheric chemistry and catalysis. Most studies have focused on hematite, α-Fe(2)O(3), as it is the thermodynamic stable state of iron oxide; however, other forms of Fe(2)O(3) naturally occur and may have different chemistries. In this study, we have investigated the reaction products and kinetics for NO(2) reacting with γ-Fe(2)O(3) powder using diffuse reflectance infrared Fourier transform spectroscopy and compared the results to those of previous studies of NO(2) reacting with α-Fe(2)O(3). Both α- and γ-Fe(2)O(3) produce surface-bound nitrate at the pressures examined in this study (24-212 mTorr); surface-bound nitrite products are observed at all pressures for γ-Fe(2)O(3) whereas nitrite was only observed on α-Fe(2)O(3) at lower pressures. Surface-bound NO(+) and Fe-NO products are observed on γ-Fe(2)O(3), which have not been observed with α-Fe(2)O(3). The reaction kinetics show a first-order dependence on NO(2) pressure and this is used to support the hypothesis of unimolecular reaction of adsorbed NO(2) with the γ-Fe(2)O(3) surface as the slow step in the reaction mechanism. The difference in product formation between NO(2) reacting with γ-Fe(2)O(3) and previous studies of α-Fe(2)O(3) illustrate the fact that care must be taken in generalizing reactivity of different polymorphs.     

不同晶化度γ-FeOOH的合成及其液相转化研究

进行了空气氧化Fe(OH)2悬浮液, EDTA作用下可见光诱导, 不同温度(14～20 ℃)制备不同晶化度γ-FeOOH的研究, 进行了其沸腾回流液相转化历程的探讨. 结果表明: 随温度的升高, γ-FeOOH的晶化程度变差; 而γ-FeOOH的晶化程度越差, 在液相沸腾回流时就越易转化成α-Fe2O3, 反之则易转化为α-FeOOH. 在pH近中性, 微量Fe(II)存在条件下低晶态的γ-FeOOH可以快速转化为均匀球形的α-Fe2O3.     

Iron oxyhydroxide nanoparticles formed by forced hydrolysis: dependence of phase composition on solution concentration

Nanoparticles of single-phase lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) have been synthesized by forced hydrolysis of ferric nitrate with no other additives, and the particles have been characterized by XRD, FT-IR and TEM. At low Fe(NO(3))(3) concentrations the hydrolysis product is predominantly γ-FeOOH, while at high concentrations it is α-FeOOH. These particles are nanometers in size and fall within narrow particle size distributions. The dependence of the oxyhydoxide phase on ferric nitrate concentration is attributed to two thermodynamic factors, the enthalpy of formation and the surface enthalpy of hydration at the oxide-water interface (which is a function of surface area). Two potential mechanisms for the phase-specific growth are proposed that explain the solution concentration dependence of the phase formed. Three other common nanoscale particles (α-Fe(2)O(3), Fe(3)O(4) and γ-Fe(2)O(3)) have also been prepared by relatively simple thermal/chemical treatment of the γ-FeOOH nanoparticles.     

ChemInform Abstract: Characterization of Iron Oxide-Dispersed Activated Carbon Fibres (ACP) with Fe K-Edge XANES and EXAFS and with Water Adsorption.

The spectra indicate that ultrafine α-FeOOH-particles transform into α-Fe2O3-like particles after vacuum heating at 573 and 773 K. The water adsorption isotherms on α-FeOOH dispersed ACF are of type V. The isotherms are analyzed by use of the Dubinin-Serpinsky equation.     

Activation energies for the rate-limiting step in water photooxidation by nanostructured α-Fe2O3 and TiO2

Competition between charge recombination and the forward reactions required for water splitting limits the efficiency of metal-oxide photocatalysts. A key requirement for the photochemical oxidation of water on both nanostructured α-Fe(2)O(3) and TiO(2) is the generation of photoholes with lifetimes on the order of milliseconds to seconds. Here we use transient absorption spectroscopy to directly probe the long-lived holes on both nc-TiO(2) and α-Fe(2)O(3) in complete PEC cells, and we investigate the factors controlling this slow hole decay, which can be described as the rate-limiting step in water oxidation. In both cases this rate-limiting step is tentatively assigned to the hole transfer from the metal oxide to a surface-bound water species. We demonstrate that one reason for the slow hole transfer on α-Fe(2)O(3) is the presence of a significant thermal barrier, the magnitude of which is found to be independent of the applied bias at the potentials examined. This is in contrast to nanocrystalline nc-TiO(2), where no distinct thermal barrier to hole transfer is observed.     

氮掺杂石墨烯与g-C3N4二维异质体对纳米Fe2O3光催化剂的复合改性

使用相分离的水解-溶剂热法制备了α-Fe₂O₃纳米粒子, 通过简单的湿化学法实现了质量分数为3%的石墨烯、 氮掺杂石墨烯和g-C₃N₄ 3种二维异质体对纳米α-Fe₂O₃的复合改性, 并比较了3种二维异质体对α-Fe₂O₃光催化活性的影响. 结果表明, 在光催化还原二氧化碳和降解液相苯酚过程中, 二维异质体的复合均提高了纳米α-Fe₂O₃的光催化活性, 氮掺杂石墨烯对α-Fe₂O₃的改性效果优于石墨烯, 其中g-C₃N₄对α-Fe₂O₃的改性效果最优. 通过表面光电压谱、 光电化学及羟基自由基等测试, 确认二维异质体的复合改性主要通过促进纳米α-Fe₂O₃的光生电荷分离和提高活性中间组分(羟基自由基)的含量提高纳米α-Fe₂O₃的光催化活性.     

单分散α-Fe_2O_3纳米结构空心亚微球的制备及表征

采用一种新的溶液生长法结合多步包覆法在自制的不同粒径SiO2单分散亚微球表面包覆不同厚度的β-FeOOH涂层,得到单分散β-FeOOH/SiO2核壳结构亚微球.实验结果表明,SiO2核心颗粒尺寸对表面涂层的形态和包覆均匀性有很大影响.当SiO2核心颗粒的平均粒径为250 nm左右时,β-FeOOH表面涂层均匀,颗粒间团聚较少,一次包覆后涂层厚度约为35 nm.涂层中β-FeOOH纳米棒的尺寸随着所选SiO2核心颗粒粒径的增大而相应增大.经多次包覆能够显著提高涂层的厚度,3次包覆后β-FeOOH表面涂层厚约100 nm.β-FeOOH/SiO2核壳结构亚微球与质量分数5%的NaOH溶液反应后,于600℃焙烧2 h得到了单分散α-Fe2O3空心微球.单分散α-Fe2O3空心亚微球表层是由α-Fe2O3纳米棒搭建而成的三维网络结构,α-Fe2O3纳米棒的尺寸与核壳结构中β-FeOOH纳米棒的尺寸基本一致.     

Rational solution growth of α-FeOOH nanowires driven by screw dislocations and their conversion to α-Fe2O3 nanowires

We report the rational synthesis of α-FeOOH (goethite) nanowires following a dislocation-driven mechanism by utilizing a continuous-flow reactor and chemical equilibria to maintain constant low supersaturations. The existence of axial screw dislocations and the associated Eshelby twist in the nanowire product were confirmed using bright-/dark-field transmission electron microscopy imaging and twist contour analysis. The α-FeOOH nanowires can be readily converted into semiconducting single-crystal but porous α-Fe(2)O(3) (hematite) nanowires via topotactic transformation. Our results indicate that, with proper experimental design, many more useful materials can be grown in one-dimensional morphologies in aqueous solutions via the dislocation-driven mechanism.     

一种新型纺锤状α-Fe_2O_3纳米晶的合成、表征及其表面性能(英文)

合成了一种新型的具有单晶结构的α-Fe2O3纳米晶(NFO-1).在我们的合成方法中,样品的形貌和结构在低反应浓度体系中运用无机盐和有机模板进行双重调控,同时用溶剂挥发诱导自组装(EISA)来加速反应和在不改变形貌结构的前提下获得高产率样品.所得α-Fe2O3纳米晶的形貌和结构对其表面修饰功能有明显的影响,NFO-1因其特殊的纺锤状形貌而与表面功能试剂(多巴胺)之间的化学作用有明显的增强.并且,本文所描述的合成方法同样适用于其他过渡金属氧化物纳米单晶的合成.我们预期,这种方法可为新型纳米材料的合成提供新的途径.     

SiO2/α-FeOOH和SiO2/γ-Fe2O3微粒的界面研究

α－FeOOH微粒由于其表面高活性，在转变成γ－Fe2O3的热处理过程中容易烧结，一旦这种烧结现象发生，得到的γ－Fe2O3磁粉磁性能大大下降[1]．为了克服这一困难，目前采用在α-FeOOH微粒表面包敷有机物[2]和无机物[3]来隔离颗粒，阻止其聚集．其中SiO2表面包敷处理是最令人感兴趣的研究课题之一[4，5]．SiO2是一种难烙性的非磁性材料，它包敷在α-FeOOH微粒表面外，不仅可提高α－FeOOH转变成γ－Fe2O3的热处理温度，有利于得到外形完好、晶格完整的γ－Fe2O3磁粉，而且由包效层与内核之间的界面相互作用引起的表面各向异性常…     

介孔α-Fe2O3表面配合反应平衡常数测定

采用十二胺为模板剂、氨水做沉淀剂成功制备了介孔α-Fe2O3,通过粉末X射线衍射(XRD)、透射电镜(TEM)、N2吸附/脱附技术对样品晶相、形貌和比表面积进行了表征.根据介孔α-Fe2O3悬浮液的酸碱滴定数据,使用FITEQL软件,采用双电层恒电容模型计算得出了介孔α-Fe2O3的表面酸碱反应平衡常数.在此基础上研究了Cu2+,Pb2+,Zn2+在介孔氧化铁表面的吸附行为,使用WinSGW软件模拟得出了相应的表面配合反应平衡常数并讨论了其吸附机理.     

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.     

Density Functional Study of the C Atom Adsorption on the α-Fe2O3 （001） Surface

The adsorption of C atoms on the α-Fe2O3(001) surface was studied based on density function theory(DFT) ,in which the exchange-correlation potential was chosen as the PBE(Perdew,Burke and Ernzerhof) generalized gradient approximation(GGA) with a plane wave basis set. Upon the optimization on different adsorption sites with coverage of 1/20 and 1/5 ML,it was found that the adsorption of C atoms on the α-Fe2O3(001) surface was chemical adsorption. The coverage can affect the adsorption behavior greatly. Under low coverage,the most stable adsorption geometry lied on the bridged site with the adsorption energy of about 3.22 eV;however,under high coverage,it located at the top site with the energy change of 8.79 eV. Strong chemical reaction has occurred between the C and O atoms at this site. The density of states and population analysis showed that the s,p orbitals of C and p orbital of O give the most contribution to the adsorption bonding. During the adsorption process,O atom shares the electrons with C,and C can only affect the outermost and subsurface layers of α-Fe2O3;the third layer can not be affected obviously.     

α-Fe(Ga)OOH的液相催化合成及表征

采用液相催化相转化法, 以Fe(III)与Ga(III)的共沉淀为前驱物合成了α-Fe(Ga)OOH微粒. 探讨了镓离子的掺杂浓度和Fe(II)离子用量等因素对合成α-Fe(Ga)OOH微粒的影响, 并对产物进行了X射线衍射(XRD)、红外光谱(IR)、扫描电镜(SEM)、透射电镜(TEM)、电子衍射(ED)表征. 结果表明: 初始pH＝9, nFe(II)/nFe(III)＝0.02, nGa(III)/nFe(III)＝0.18时, 在沸腾回流条件下可制备出类多面体形的α-Fe(Ga)OOH微粒, 镓离子的掺杂对α-FeOOH的形成起了形貌调控作用, 电子衍射数据表明该α-Fe(Ga)OOH为单晶粒子.