核磁共振弛豫速率方法测定模拟正铁色素的结构

在生命体系内正铁色素具有摄铁和输铁的功能,人工合成的模拟化合物具备了正铁色素的主要功能基团和相近的性质.本工作利用铁(Ⅲ)离子的顺磁性质,测定不同铁(Ⅲ)离子浓度下模拟正铁色素的诱导弛豫时间,根据简化了的Solomon—B1oemoergen公式,计算出铁(Ⅲ)离子到所有被测质子(即氢原子)的相对距离,比较清楚地得到模拟正铁色素在溶液中的构象。     

痕量铁(Ⅲ)的催化光度法测定及动力学机制研究

在0.30 mol·L-1盐酸中,铁(Ⅲ)显著催化过硫酸钾氧化甲基红的褪色反应,据此建立了测定痕量铁(Ⅲ)的“Fe(Ⅲ)-盐酸-过硫酸钾-甲基红”新体系,研究了该体系测定痕量铁(Ⅲ)的最佳条件,考察了共存离子对测定的影响,分析了测定反应的动力学参数及方程,并利用动力学性质探讨了测定痕量铁(Ⅲ)的反应机理,从而构建了一种测定痕量铁(Ⅲ)的新催化动力学光度法。研究表明,在最大吸收波长518 nm以及最佳测定条件下,该体系中甲基红的浓度变化与铁(Ⅲ)含量呈以下良好线性关系：ln(A₀/A)=1.334 1+0.001 0,相关系数为0.999 1;痕量铁(Ⅲ)发生一级反应,该测定体系符合准一级反应特征且反应的表观活化能为69.88 kJ·mol-1;反应机理的研究进一步证明了该体系中痕量铁(Ⅲ)起催化作用;该痕量铁(Ⅲ)的测定方法操作简便,所用试剂廉价易得,目前还未见报道,其灵敏度优于普通光度法,检出限达0.005 mg·L-1。该方法应用于实测水样和食品中痕量铁(Ⅲ),相对标准偏差为1.18%～2.11%,平均回收率为98.0%～104.0%。该测定体系稳定,结果满意。     

邻苯二酚荧光光谱法测定铁(Ⅲ)的研究

基于铁(Ⅲ)对荧光试剂邻苯二酚的荧光熄灭,建立了测定微量铁的荧光分析方法.在0.3mol/L的HCl介质中,最大激发与发射波长分别为277nm和313nm,铁的荧光强度与浓度呈良好的线性关系,测定铁浓度的线性范围为1.59×10-5-1.26×10-3mol/L,检出限为7.14×10-6mol/L,常见的共存离子不干扰测定.本方法用于环境水中铁(Ⅲ)的测定,结果满意.     

利用铁（Ⅲ）—硫代硫酸盐反应催化法测定铜（Ⅱ）及其在金属和生物样品分析中的应用

拟定了在没有硫氰酸盐,并且铁的浓度远大于硫代硫酸盐的条件下,应用铁(Ⅲ)-硫代硫酸盐反应催化测定铜(Ⅱ)的分光光度法。获得了轮廓分明的吸收光谱,并且讨论了不稳定的铁(Ⅲ)-硫代硫酸盐络合物的褪色反应。发现了铁(Ⅲ)及其它外来离子对测定只有轻微的影响。铜的校准曲线的线性范围是0-2.0微克,1.0微克铜五次测定的标准偏差是0.036微克,检测限约0.05微克。该法已成功地应用于一些金属和生物样品的分析,无需任何分离。关键词:铜的测定;催化法;铁(Ⅲ)硫代硫酸盐反应;金属;生物样品。根据铁(Ⅲ)-硫代硫酸盐催化反应而建立的目测或光电光度计测定铜已有报导     

取代铁卟啉的拉曼及红外光谱分析

合成了系列取代铁卟啉化合物,研究了拉曼光谱及红外光谱.对二价铁卟啉RTPPFe(Ⅱ)和三价铁卟啉RTPPFeCl(Ⅲ)的红外光谱和拉曼光谱进行了对比分析,结果表明,二价铁卟啉在常温下是不稳定的,通常在其轴向位置上吸附氧分子而形成铁卟啉的超氧化物RTPPFe-O2,其稳定的立体构型为end-on式结构.采用量化软件对化合物的分子结构进行了模拟,得出了其分子结构参数,并结合化合物的红外及拉曼光谱,研究了分子结构对波谱位移的影响.不同结构的二价铁卟啉RTPPFe-O2拉曼及红外吸收峰的位置发生了不同程度的位移,其位移情况与分子的扭曲程度有关.即RTPPFe-O2的Fe-O2特征拉曼吸收峰以及红外特征吸收峰(Fe-O)的位置随着Fe-O-O角的增大而向高波数移动.     

酸性品红褪色光度法测定痕量铁(Ⅲ)

基于Fe(Ⅲ)可使酸性品红氧化褪色,建立了一种褪色光度法测定铁的新方法,该方法线性范围为0-8.25μg/mL,检出限为3.72×10-4μg/mL.用于水样中Fe(Ⅲ)含量的测定,回收率在90%-100%.     

螯合剂对稀土-转铁蛋白配合物的影响Ⅲ柠檬酸脱除TbC-Tf中铽(Ⅲ)的动力学研究

通过监测人血清脱铁转铁蛋白C-端结合部位结合铽(Ⅲ)(TbC-Tf)在549 nm处荧光强度随时间的变化, 在0.1 mol·L-1 Hepes, pH 7.4及室温条件下观察了柠檬酸对人血清脱铁转铁蛋白结合铽(Ⅲ)的脱除. 结果表明, 柠檬酸对人血清脱铁转铁蛋白结合铽(Ⅲ)的脱除有两种途径: 饱和动力学和一级反应动力学途径.     

一阶导数光谱法同时测定石英砂中铁和铝的研究

研究了在pH＝6.0的HAc-NaAc缓冲体系中，Al(Ⅲ)和Fe(Ⅲ)分别与乙二醇二乙醚二氨基四乙酸（EGTA），邻苯三酚红（PR），溴化十六烷基吡啶（CPB）形成的四元络合物的性质，利用一阶导数光谱法对微量铁和铝进行了同时测定，测定的变异系数分别为4.5%和1.1%，加标回收率分别为93－98％和95－102％,方法可用于石英砂中微量铁和铝的测定。     

铁小檗碱化合物结构的密度泛函理论研究

本工作采用密度泛函理论(B3LYP)方法对铁小檗碱化合物的中性分子及离子进行了结构优化和频率计算.结果表明:无论是中性分子还是离子,铁小檗碱物化合物基态结构都是小檗碱基态结构中的与N原子相邻的C10原子上键合一个Fe原子形成的.其阳离子结构具有C_1对称性和~3A电子态;中性分子的基态结构具有C_1对称性和2A电子态;阴离子的基态结构具有C1对称性和5A电子态.当铁小檗碱物化合物的阳离子得到一个电子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所变短;当中性分子得到一个电子变成阴离子后,C(10)-Fe(26)及Fe(26)-H(44)的键长都有所增加.     

FeSe基超导体的探索与物性研究

自从2008年铁基超导体发现以来,人们探索并发现了一系列的铁基高温超导材料,其中FeSe基超导体因其具有的独特性质而引起了人们的广泛关注.本文主要介绍了两类新的铁基超导体,即水热合成法合成的（Li,Fe）OHFeSe及电化学插层方法合成的（CTA）_xFeSe的晶体结构及超导性质;对近年发展起来的利用电双层场效应晶体管技术以及固态离子导体调控FeSe的电子态性质的研究做了简要介绍.     

一个催化氧化四甲基联苯胺荧光测定超痕量铁的新方法

铁是一种必需的微量元素,它在生命过程中起着重要的作用,但是摄入过多的三价铁会使机体的载氧能力下降,引起不稳定血红蛋白病以及高铁血红蛋白症等疾病。无论是从人类健康还是环境保护角度出发,探究简便、快速、灵敏度高和选择性好的检测Fe（Ⅲ）的分析新方法很有意义。荧光分析是一种优异的分子光谱分析方法,具有灵敏度高、选择性强、操作简单等特点,在重金属离子的检测方面也取得了较好的进展,目前利用荧光法测定Fe3+也有报道,但有的灵敏度不高,有的选择性不好,有的试剂毒性较大。报道了一种简单、快速、灵敏检测Fe（Ⅲ）的四甲基联苯胺（TMB）荧光分析新方法。在pH 4.5 Tris-HCl缓冲液及35 ℃水浴条件下,H₂O₂氧化无毒易得的四甲基联苯胺（TMB）这一反应较慢;当有痕量Fe（Ⅲ）存在时,它催化过氧化氢（H₂O₂）氧化TMB生成具有较强荧光活性的TMB氧化产物（TMB_ox）,用激发波长280 nm激发,TMB_ox在405 nm处有一个较强的荧光峰,且在一定的范围内,随着Fe（Ⅲ）浓度的增大,其荧光强度线性增强。采用单变量变换法优化了荧光分析条件,选择Tris-HCl缓冲溶液的pH为4.5,其浓度为3.3×10-4 mol·L-1,TMB浓度为3.0×10-5 mol·L-1,H₂O₂浓度为6.0×10-6 mol·L-1,在35 ℃条件下反应35 min。在选定条件下,Fe3+浓度在0.027～400 nmol·L-1范围内,随着Fe3+浓度的增大,体系在405 nm处的荧光信号线性增强,其线性方程为ΔF_{405 nm}=2.31c+5.0,线性相关系数R2为0.985,其检出限为0.008 nmol·L-1。考察了共存物质对测定200 nmol·L-1 Fe（Ⅲ）的影响。结果表明,当相对误差在±10%之内,20 μmol·L-1的HCO-₃,K+,SO2-₄,NH+₄,Mn2+,Na+,Cu2+,Al3+,Zn2+,F-,Mg2+,Ba2+,Ca2+,Co2+,NO3-,NO2-,10 μmol·L-1的CO2-₃,Cr6+,2 μmol·L-1的Hg2+,BSA不干扰测定。表明该法具有较好的选择性。据此,建立了一个简单、快速、灵敏高、选择性高的测定Fe（Ⅲ）的荧光分析新方法。按以下步骤制备了乳制品的样品溶液,准确吸取1.4 mL乳制品加入600 μL乙酸（V/V=3％）,于10 000 r·min-1下离心3 min,然后吸取离心上清液1mL加入48 μL 2.5 mol·L-1 NaOH定容至2 mL,于10 000 r·min-1下离心3 min,最后吸取1 mL上清液稀释至5 mL得到样品溶液。然后采用该催化荧光分析新方法测定了牛奶样品中Fe（Ⅲ）含量,结果令人满意, 其相对标准偏差为0.29%～0.41%,回收率为94.6%～108.0%。     

First-principles Study on the Magnetic,Half-metal and Thermoelectric Transport Properties of Inorganic-Organic Hybrid Compounds [C4N2H12][Fe4Ⅲ(HPO3)2(C2O4)3]

The electronic structure, magnetic and half-metal properties of inorganic-organic hybrid compound [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] are investigated by using the full-potential linearized augmented plane wave (FPLAPW) method within density-functional theory (DFT) calculations. The density of states (DOS), the total energy of the cell and the spontaneous magnetic moment of [C₄N₂H₁₂][Fe₄^Ⅱ(HPO₃)₂(C₂O₄)₃] are calculated. The calculation results reveal that the low-temperature phase of [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] exhibits a stable ferromagnetic (FM) ground state, and we find that this organic compound is a half-metal in FM state. In addition, we have calculated antiferromagnetically coupled interactions, revealing the existence of antiferromagnetic (AFM), which is in agreement with the experiment. We have also found that [C₄N₂H₁₂][Fe₄^Ⅲ(HPO₃)₂(C₂O₄)₃] is a semiconductor in the AFM state with a band gap of about 0.40 eV. Subsequently, the transport properties for potential thermoelectric applications have been studied in detail based on the Boltzmann transport theory.     

Comparative analysis of the 1H NMR relaxation enhancement produced by iron oxide and core-shell iron-iron oxide nanoparticles

Physicochemical and magnetorelaxometric characterization of the colloidal suspensions consisting of Fe-based nanoparticles coated with dextran have been carried out. Iron oxide and iron core/iron oxide shell nanoparticles were obtained by laser-induced pyrolysis of Fe(CO)₅ vapours. Under different magnetic field strengths, the colloidal suspension formed by iron oxide nanoparticles showed longitudinal (R₁) and transverse (R₂) nuclear magnetic relaxation suspension (NMRD) profiles, similar to those previously reported for other commercial magnetic resonance imaging (MRI) contrast agents. However, colloidal suspension formed by ferromagnetic iron-core nanoparticles showed a strong increase of the R₁ values at low applied magnetic fields and a strong increase of the R₂ measured at high applied magnetic field. This behaviour was explained considering the larger magnetic aggregate size and saturation magnetization values measured for this sample, 92 nm and 31 emu/g Fe, respectively, with respect to those measured for the colloidal suspensions of iron oxide nanoparticles (61 nm and 23 emu/g Fe). This suspension can be used both as T₁ and T₂ contrast agent.     

First-principles study of the structural,electronic, and magnetic properties of double perovskite Sr_2FeReO_6 containing various imperfections

The structural, electronic, and magnetic properties of double perovskite Sr_2FeReO_6 containing eight different imperfections of FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges, V_(Fe), V_(Re), VOor V_(Sr) vacancies have been studied by using the first-principles projector augmented wave(PAW) within generalized gradient approximation as well as taking into account the on-site Coulomb repulsive interaction(GGA+U). No obvious structural changes are observed for the imperfect Sr_2FeReO_6 containing FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges, or VSrvacancy defects. However, the six(eight) nearest oxygen neighbors of the vacancy move away from(close to) VFeor V_(Re)(VO) vacancies. The half-metallic(HM) character is maintained for the imperfect Sr_2FeReO_6 containing FeReor ReFeantisites, Fe1–Re4 interchange, V_(Fe),VO or V_(Sr) vacancies, while it vanishes when the Fe1–Re1 interchange or VRevacancy is presented. So the Fe1–Re1 interchange and the VRevacancy defects should be avoided to preserve the HM character of Sr_2FeReO_6 and thus usage in spintronic devices. In the FeReor ReFeantisites, Fe1–Re1 or Fe1–Re4 interchanges cases, the spin moments of the Fe(Re)cations situated on Re(Fe) antisites are in an antiferromagnetic coupling with those of the Fe(Re) cations on the regular sites. In the V_(Fe), V_(Re), VO, or V_(Sr) vacancies cases, a ferromagnetic coupling is obtained within each cation sublattice,while the two cation sublattices are coupled antiferromagnetically. The total magnetic moments μtot(μB/f.u.) of the imperfect Sr_2FeReO_6 containing eight different defects decrease in the sequence of VSrvacancy(3.50), VRevacancy(3.43),FeReantisite(2.74), VOvacancy(2.64), VFevacancy(2.51), ReFeantisite(2.29), Fe1–Re4 interchange(1.96), Fe1–Re1interchange(1.87), and the mechanisms of the saturation magnetization reduction have been analyzed.     

Pulsed wire discharge for nanosize powder synthesis

The pulsed wire discharge, as one of the well-developed pulsed power technologies, has been successfully applied to nanosize powder production. In the demonstration experiments, the discharge was carried out with the peak current of ~10 kA, the pulse length of ~20 μs, and the pulse energy of ~80 J. Nanosize powders of metals (Al, Fe, Cu, Mo, and Pb), metal oxides (Al₂O₃, TiO₂, Fe ₂O₃, NiO, ZrO₂, SnO₂, and PbO), and metal nitrides (TiN, ZrN, Ta₂N) have been synthesized by pulsed discharge of metal wires in argon, oxygen, or nitrogen. The typical powder production rate was ~5 mg/pulse. The results of surface-area measurement have given the average powder sizes in the range of 20~70 nm, depending on the material of the powder     

杭锦2#土的光谱特征及非均相Fenton反应机理

杭锦2#土是内蒙古鄂尔多斯杭锦旗地区发现的层状含铁天然矿物,利用Ｘ射线衍射、吡啶吸附红外光谱及Ｘ射线光电子能谱技术对样品的性质进行了表征。X射线光电子能谱表明杭锦2#土骨架结构中Si和Al原子结合能与标准硅氧四面体和铝氧八面体中Si和Al结合能相比明显增加,表面存在Lewis酸位和Brönsted酸位,且杭锦2#土中铁物种以Fe(Ⅲ)和Fe(Ⅱ)形式存在于骨架结构中;非均相Fenton反应中杭锦2#土的Fe(Ⅱ)可与H₂O₂反应生成自由基(·OH)与Fe(Ⅲ),但反应速率慢且难以循环。酸活化后杭锦2#土中Si和Al的结合能进一步增加,铁物种部分转变为非结构铁并以Fe3+与Fe2+转移到样品表面;X射线光电子能谱、吡啶红外和氨气程序升温表征表明酸活化杭锦2#土表面Lewis酸位和Brönsted酸位增多;非均相Fenton反应中,酸活化杭锦2#土表面Fe3+与Fe2+可与H₂O₂循环反应,不断生成·OH并对甲基橙进行降解,且活化杭锦2#土表面Brönsted酸能够提供质子将H₂O₂包围,抑制其分解生成HO-₂并提供更多的·OH,Lewis酸能增加杭锦2#土表面吸附氧（O_ad）含量,而Fe2+可被O_ad氧化为Fe3+,促进Fe2+/Fe3+之间的循环,同时在氧化过程中电子转移到O_ad形成O·-₂,O·-₂能够与Brönsted酸提供的质子反应形成·OH,·OH与O·-₂均为氧化性自由基,能够提升活化杭锦2#土非均相Fenton反应活性。此外,X射线衍射表明酸活化使杭锦2#土中CO2-₃转化为对Fenton反应负面影响更小的SO2-₄进而提升其非均相Fenton反应活性。     

Kinetic interface roughening and magneto resistance of sputter-deposited Fe/Ni75B25 multilayers

The roughening of interfaces as a function of layer thickness and magneto transport properties have been investigated on sputter-deposited Fe/Ni₇₅B₂₅ multilayer films. X-ray reflectivity data were recorded for Ni₇₅B₂₅(72 nm) film and for [Fe(2 nm)/Ni₇₅B₂₅(2 nm)]₁₆ and [Fe(4 nm)/Ni₇₅B₂₅(4 nm)]₈ multilayer films. A power law dependence of the interfacial width of growing Fe/Ni₇₅B₂₅ interfaces was observed. The resulting growth exponents β were found to be in the range of 0.55–0.58 in the initial growth stage of the multilayer with lower Fe/Ni₇₅B₂₅ repetition thickness and at approximately 0.34 for multilayer with higher repetition thickness. The growth exponents were compared with theoretical calculations. High resolution electron microscopy revealed the columnar growth of the Fe/Ni₇₅B₂₅ multilayer. Additionally, an increase of magnetoresistance was observed by the multilayering of Ni₇₅B₂₅ films with Fe interlayers.     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于sp³杂化C-H键的对称伸缩振动和反对称伸缩振动的红外特征峰2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.     

Fe(Ⅲ)对脂肪酸13C NMR信号的影响

研究了Fe (Ⅲ)对脂肪酸¹³C NMR信号的影响.结果表明,Fe (Ⅲ)对脂肪酸¹³C NMR信号的影响的机理是电子自旋弛豫对核自旋弛豫的影响;产生这种影响的必要条件是Fe (Ⅲ)与脂肪酸之间的缔合.该影响沿化学键传递并随距离的增加而迅速衰减.破坏Fe (Ⅲ)与脂肪酸之间的缔合,可使这种影响消失.利用该现象可帮助某些化合物¹³C NMR信号的归属,并可对某些分子在溶液中的状态进行研究.     

Average and local magnetic moments on Fe atoms in microcrystalline and amorphous Fe100−xPx alloys

We have measured the concentration dependence of the average magnetic moment per Fe atom _Fe(x) in microcrystalline and amorphous Fe-P alloys obtained over a wide concentration range using electrochemical deposition. The model of local magnetic moments has been used to described _Fe(x). On the basis of this model the effects of phosphorus on the value _Fe are explained in terms of the parameters of the local environment of the Fe atom.