Solvent and pH Effects on the Fluorescence of 7-(Dimethylamino)-2-Fluorenesulfonate

A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless single band with a large Stokes shift, whereas that of the acidic form, *(⁺HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(⁺HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant advantages for a variety of applications.     

Solvent effects on the static nuclear relaxation and the curvature hyperpolarizabilities of push-pull polyenes

The influence of the solvent on the nuclear relaxation and curvature contributions to the first, β, and second, γ, hyperpolarizability, of push-pull molecules has been investigated within the framework of the valence-bond charge-transfer model and the analytical evaluation of electrical properties method. It was found that the solvent effect on the β and γ values is very pronounced, where increases of a factor as great as 15 for cyanine resonance form and 30 for zwitterionic and neutral resonance forms, were calculated upon changing from gas phase to an aqueous environment. The general trends of β and γ in different environments may be estimated roughly by adding the harmonic terms of the nuclear relaxation to the electronic contribution because the anharmonics terms of the nuclear relaxation and the contribution of curvature tend to cancel one another.     

General and Specific Solvent Effects in Optical Spectra of <Emphasis Type="Italic">ortho</Emphasis>-Aminobenzoic Acid

We describe studies about solvent effects on the absorption and emission properties of o-aminobenzoic acid (o-Abz), interpreting the results within the framework of general and specific solute-solvent interactions. Measurements were performed in several solvents and analysis of the absorption and emission wavelengths were made based on Lipperts model for general solvent effects and on the use of different parameters to describe the ability of the solvent to promote specific interactions with the solute. We observed low sensitivity of the Stokes shift upon changes in the medium polarity, and large deviation from the linearity predicted by Lipperts equation when the solvents were characterized as Bronsted acid in the Kamlet-Taft ^* scale. Quantum yield and fluorescence lifetimes were best interpreted based on the AN+DN scale used to describe the electron donor/acceptor properties of the solvent. The results indicated that non-radiative deexcitation processes are favoured in solvents which promote the formation of intramolecular hydrogen bond, while interactions with electron acceptor solvents lead to enhancement of fluorescence.     

逐级溶剂处理对子长煤有机质大分子结构的影响

从分子水平上理解低阶煤有机质大分子结构的解聚和解离是对其进行高效利用并从中获取高附加值化学品亟需解决的关键问题.为了探究煤有机质大分子结构的解聚和解离机理,借助核磁共振碳谱(13 C NMR)、X射线光电子能谱技术(XPS)以及热重分析(TG/DTG)对经过常温超声萃取、醇解、催化醇解逐级溶剂处理的子长低阶煤的化学结构...     

High-energy proton-irradiation effects on the charge transport and electric dipole moment of KH2PO4

We have studied the charge transport and dielectric properties of KH₂PO₄ (KDP) single crystals, irradiated by proton beams with high energies up to 20 MeV, by means of the temperature-dependent electrical conductivity and dielectric constant measurements. It is shown that the electrical conductivity and the electric dipole moment may be sensitively controlled by the proton irradiation energy and dose. The activation energy and the dipole moment were shown to be strongly correlated.     

基于可见光-近红外光谱的BIF磁性率确定方法研究

铁矿中磁性率是评价铁矿床工业价值和划分矿石工业类型的重要指标。传统的磁性率测定法存在工作量大、效率低、周期长的缺陷,成为经济、合理、高效开采铁矿资源的瓶颈问题。采用便携式地物光谱测试仪对辽宁省鞍钢集团鞍千矿业有限责任公司的BIF实验样品进行可见光-近红外光谱测试,分析了光谱特征,构建了比值指数(RI)、差值指数(DI)和归一化指数(NDI),并确定光谱指数与样品磁性率相关性最显著的敏感波段及对应的相关系数值;优选出与样品磁性率相关性最显著的比值指数(RI),构建实验样品磁性率的定量反演模型,并进行了验证。结果表明,三种光谱指数与样品磁性率敏感波段均位于935与1 050 nm,且该波段处的相关系数均达到0.9以上,其中比值指数与样品磁性率的相关性最高;基于比值指数构建的实验样品磁性率定量反演模型的预测误差为0.038,反演磁性率与实测磁性率的判定系数(R2)为0.964 5,预测结果比较理想。为确定BIF的磁性率提供了一种新方法,该方法具有工作强度小、经济、高效、便捷的优点,且对遥感找矿具有一定指导意义。     

溶剂对香豆素343染料光谱性质和最低激发态偶极矩的影响

通过对香豆素343(C343)在不同溶剂中的稳态吸收光谱、稳态荧光光谱和时间分辨荧光光谱的分析,研究了溶剂对C343的光谱性质的影响,并获得了光谱特性与溶剂极性之间的依赖关系. 吸收光谱峰值的红移随着溶剂极性的增加而发生较小的变化. 然而,荧光光谱的峰值对溶剂的极性却很敏感,并随着溶剂极性参数f(ε,n)的增加呈线性增长. 这是由于C343激发态电荷分布的变化导致了它在极性溶剂中第一激发单重态能级的变化. 用溶剂效应测量法和量子化学计算方法确定了C343最低激发态的偶极矩,这两方法所得的结果一致. C343在不同溶剂中的时间分辨荧光光谱研究表明荧光寿命随着溶剂极性的增加而增加,即从甲苯溶液的3.09 ns线性地增加到水溶液中4.45 ns;荧光寿命延长的根源可归因于C343与氢键给体溶剂之间的分子间氢键相互作用.     

Fluorometric investigation of the interaction between nitrophenols and 7-hydroxy-4-azidomethylcoumarin

The interaction between nitrophenols and 7-hydroxy-4-azidomethylcoumarin has been investigated by fluorescence and UV-vis absorbance spectroscopy. Quenching mechanisms have been evaluated by fluorescence measurements at different temperatures. Stern-Volmer quenching constant K_sv and corresponding thermodynamic parameters ΔH⁰, ΔG⁰ and ΔS⁰ were calculated. Binding studies concerning the number of binding sites ‘n’ and apparent binding constant ‘K’ were performed by fluorescence quenching method.     

Effects of junction parameters on the resonant macroscopic quantum tunnelling in small Josephson junctions

Summary Within the well-established quantum picture of a Josephson junction, it has been shown that the possibility of a resonant macroscopic quantum tunnelling can produce sharp voltage peaks in the current-voltage characteristics. We investigate the effects of the junction parametrs and bias conditions on the step amplitude, in view of an experimental check of the proposed phenomenon.     

基于可见-近红外和热红外光谱联合分析的煤和矸石分类方法研究

煤与矸石是矿山采煤过程中主要固体堆放物,对其进行遥感动态监测是矿山环境保护的重要需求。由于煤与部分矸石存在“异物同谱”现象,在使用传统的可见-近红外遥感分类时,往往将部分矸石划分为煤,导致遥感分类精度降低。首先对铁法矿区的12个煤样本和115个矸石样本进行可见-近红外光谱测试,发现绝大部分矸石样品的光谱与煤差异很大,二者易于区分,但有部分矸石与煤样本存在“异物同谱”现象。为进一步对矸石与煤区分,测试了混分样本的热红外光谱,发现二者存在明显的光谱差异,利用热红外光谱特征可以将其区分开来。在此基础上,提出了基于可见-近红外和热红外光谱联合分析的煤与矸石区分方法。该方法首先对所有样本进行可见-近红外光谱测试,利用Mao模型进行第一步分类识别;其次对煤与矸石混分的样品进行热红外光谱测试,利用光谱吸收比率SAR作为判别指标进行第二步分类,两步的分类结果为最终分类结果。该方法在铁法、兖州、神东和木里矿区的验证结果表明,其具有很高的分类准确率,效果远好于单独基于可见-近红外光谱特征的分类方法。研究结果表明,利用多种光谱联合分析的方法可以解决单波段存在的“异物同谱”现象,对于地物遥感分类具有重要的借鉴意义。     

太赫兹波段豆油光谱的优化测量

太赫兹时域光谱技术是基于飞秒超快激光技术的有效的光谱检测技术,太赫兹波独特的优势使其成为一种有效的无损检测手段,并被广泛地应用到各个领域。然而在样品检测尤其是液体样品检测过程中,由于Fabry-Perot效应的存在,太赫兹波在样品、样品容器、以及光学元件之间的多次反射,使时域信号产生回波,样品的吸收光谱在频域内产生振荡,有可能会隐藏一些重要的吸收特征。为了解决这一问题,对解卷积算法进行改进,在传统计算模型的基础上,考虑系统中液体池窗片和光学元件对太赫兹波的非线性吸收,将包含回波的太赫兹时域信号描述为太赫兹主脉冲与一系列冲击信号和非线性传递函数的卷积。通过分析,有效去除回波引起的频谱振荡,进一步提高太赫兹波段豆油光学参数的测定精度。实验对比了改进前后0.2～2 THz波段豆油的频谱及吸收谱,实验结果证明,与传统的主脉冲截取法相比,本算法不仅能有效去除回波引起的频谱振荡,且在相同检测条件下,可将太赫兹波段豆油样品的频率分辨率由50 GHz有效提高至10 GHz。该算法不受被测对象参数的影响,同样适用于其他液体的太赫兹时域光谱测量。最后对吸收谱中残余的频谱振荡进行了深入分析。     

沉淀过程pH值对铈锆复合氧化物结构与性能的影响

采用加热回流老化技术制备了系列组成为0.6CeO₂-0.4ZrO₂的铈锆复合氧化物,通过N₂物理吸附、Raman光谱、UV-Vis 漫反射光谱等方法对沉淀过程pH值对铈锆复合氧化物结构及储氧性能的影响进行了研究。结果表明,沉淀过程pH值不同,将导致铈锆复合氧化物的组成产生波动,进而影响样品的晶相组成、缺陷性质、结晶程度和孔结构性质。控制沉淀pH值为10.5～11.0,可消除Si的影响,改善铈锆复合氧化物的孔结构,提高相均匀性,提高缺陷浓度,降低结晶度,从而可提高样品的储氧性能。     

Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of (meta‐substituted phenoxy)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄SFp ( 2 )] complexes. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G is NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao–Perdew–Staroverov–Scuseria and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free energy relations [r = 1.00 (g, 1e), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and δΔG⁰ of O?H bonds of m‐G‐C₆H₄OH or ΔΔH_het(Fe–S)'s and ΔpK_a's of S?H bonds of m‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And, the linear correlations [r = ?0.97 (g, 1 g), ?0.97 (g, 2 h)] among the ΔΔH_het (Fe–O)'s or ΔΔH_het(Fe–S)'s and the substituent σ_m constants show that these correlations are in accordance with Hammett linear free energy relationships. The inductive effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. The ΔΔH_het(Fe–O)'s(g) (1) and ΔΔH_het(Fe–S)'s(g)(2) follow the capto‐dative Principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2016 John Wiley & Sons, Ltd.     

Hartree–Fock and density functional theory study of remote substituent effects on heterolytic Fe–N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4N(COMe)Fe(CO)2(η5‐C5H5)

The nature and strength of metal–ligand bonds in organotransition‐metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–N bond energies of para‐substituted anilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄NH(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄NHFp (1), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted α‐acetylanilinyldicarbonyl(η⁵‐cyclopentadienyl)iron [p‐G‐C₆H₄N(COMe)(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–N)'s. The linear correlations [r = 0.98 (g, 1a), 0.93 (g, 2b)] between the substituent effects of heterolytic Fe–N bond energies [ΔΔH_het(Fe–N)'s] of series 1 and 2 and the differences of acidic dissociation constants (ΔpK_a) of N–H bonds of p‐G‐C₆H₄NH₂ and p‐G‐C₆H₄NH(COMe) imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1c), ?0.92 (g, 2d)] between ΔΔH_het(Fe–N)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–N)'s. ΔΔH_het(Fe–N)'s(1, 2) follow the captodative principle. ME_{α‐COMe, para‐G}s include the influences of the whole molecules. The correlation of ME_{α‐COMe, para‐G}s with σ_p^? is excellent. ME_{α‐COMe, para‐G}s rather than ΔΔH_het(Fe–N)'s in series 2 are more suitable indexes for the overall substituent effects on ΔH_het(Fe–N)'s(2). Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.     

Remote substituent effects on homolytic Fe‐N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4(COMe)NFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

The nature and strength of metal–ligand bonds in organotransition–metal complexes is crucial to the understanding of organometallic reactions and catalysis. The Fe‐N homolytic bond dissociation energies [ΔH_homo(Fe‐N)′s] of two series of para‐substituted Fp anilines p‐G‐C₆H₄NHFp [1] and p‐G‐C₆H₄N(COMe)Fp [2] were studied using the Hartree–Fock (HF) and the density functional theory methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂ and G are NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO and NMe₂. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe‐N)′s. B3LYP can also satisfactorily predict the α and remote substituent effects on ΔH_homo(Fe‐N)′s [ΔΔH_homo(Fe‐N)′s]. The good correlations [r = 0.96 (g, 1), 0.99(g, 2)] of ΔΔH_homo(Fe‐N)′s in series 1 and 2 with the substituent σ_p⁺ constants imply that the para‐substituent effects on ΔH_homo(Fe‐N)′s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH_homo(Fe‐N)′s(1,2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.     

Hartree–Fock and density functional theory study of remote substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of para‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄O(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄OFp ( 1 ), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted benzenethiolatodicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄S(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄SFp ( 2 )] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free‐energy relations [r = 0.99 (g, 1a), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and Δpk_a's of O–H bonds of p‐G‐C₆H₄OH or ΔΔH_het(Fe‐S)'s and Δpk_a's of S–H bonds of p‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1g), ?0.98 (g, 2h)] among the ΔΔH_het (Fe‐O)'s or ΔΔH_het(Fe‐S)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free‐energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. ΔΔH_het(Fe–O)'s(g) ( 1 ) and ΔΔH_het(Fe–S)'s(g)( 2 ) follow the Capto‐dative principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

Metal–ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe–O and Fe–S homolytic bond dissociation energies [ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s] of two series of para‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄OFp ( 1 )] and (para‐substituted benzenethiolato)dicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄SFp ( 2 )] were studied using Hartree–Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G are NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that DFT methods can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s. The remote substituent effects on ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s [ΔΔH_homo(Fe–O)'s and ΔΔH_homo(Fe–S)'s] can also be satisfactorily predicted. The good correlations [r = 0.98 (g, 1), 0.98 (g, 2)] of ΔΔH_homo(Fe–O)'s and ΔΔH_homo(Fe–S)'s in series 1 and 2 with the substituent σ_p⁺ constants imply that the para‐substituent effects on ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH_homo(Fe–O)'s ( 1 ) and ΔΔH_homo(Fe–S)'s ( 2 ) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

The thermochemistry of organometallic complexes in solution and in the gas phase has been an area of increasing research interest. In this paper, the Fe–O and Fe–S homolytic bond dissociation energies [ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s] of two series of meta‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄SFp ( 2 )] were studied using Hartree–Fock and density functional theory methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G are NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao–Perdew–Staroverov–Scuseria and Minnesota 2006 functionals can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s. The polar effects of the meta substituents show that the dominant role to the magnitudes of ΔΔH_homo(Fe–O)'s or ΔΔH_homo(Fe–S)'s. σ_α·, σ_c· values for meta substituents are all related to polar effects. Spin‐delocalization effects of the meta substituents in ΔΔH_homo(Fe–O)'s and ΔΔH_homo(Fe–S)'s are small but not necessarily zero. Molecular effects rather than ΔΔH_homo(Fe–O)'s and ΔΔH_homo(Fe–S)'s are more suitable indexes for the overall substituent effects on ΔH_homo(Fe–O)'s and ΔH_homo(Fe–S)'s. The meta substituent effects of meta‐electron‐withdrawing groups on the Fe–S bonds are much stronger than those on the Fe–O bonds. For meta‐electron‐donating groups, the meta substituent effects have the comparable magnitudes between series 1 and 2 . ΔΔH_homo(Fe–O)'s ( 1 ) and ΔΔH_homo(Fe–S)'s ( 2 ) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2015 John Wiley & Sons, Ltd.     

Substituent effects on gas‐phase homolytic Fe–N bond energies of m‐G‐C6H4NHFe(CO)2(η5‐C5H5) and m‐G‐C6H4N(COMe)Fe(CO)2(η5‐C5H5) studied using density functional theory methods

One of the most fundamental properties in chemistry is the bond dissociation energy, the energy required to break a specific bond of a molecule. In this paper, the Fe–N homolytic bond dissociation energies [ΔH_homo(Fe–N)'s] of 2 series of (meta‐substituted anilinyl)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄NHFp ( 1 )] and (meta‐substituted α‐acetylanilinyl)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄N(COMe)Fp ( 2 )] were studied using density functional theory methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G is NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao‐Perdew‐Staroverov‐Scuseria, Minnesota 2006, and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe–N)'s. The ΔΔH_homo(Fe–N)'s ( 1 and 2 ) conform to the captodative principle. The polar effects of the meta‐substituents show the dominant role to the magnitudes of ΔΔH_homo(Fe–N)'s. σ_α· and σ_c· values for meta‐substituents are all related to polar effects. Spin‐delocalization effects of the meta‐substituents in ΔΔH_homo(Fe–N)'s are small but not necessarily zero. RE plays an important role in determining the net substituent effects on ΔH_homo(Fe–N)'s. Insight from this work may help the design of more effective catalytic processes.     

Dependence of pH and surfactant effect in the synthesis of magnetite (Fe3O4) nanoparticles and its properties

Nanoparticles of Fe₃O₄ were synthesized by co-precipitation in an aqueous solution containing ferrous and ferric salts (1:2) at varying pH with ammonia as a base. It was found that the value of pH influences the reaction mechanism for the formation of Fe₃O₄. Furthermore, the addition of mercaptoethanol significantly reduced the crystalline size of Fe₃O₄ nanoparticles from 15.03 to 8.02 nm. X-ray diffraction (XRD) spectra revealed that the synthesized nanoparticles were ε-Fe₂O₃ or Fe₃O₄ phase. To further prove the composition of the product, as-prepared Fe₃O₄ were examined by X-ray photoelectron spectroscopy (XPS). Magnetic properties of the obtained particles were determined by vibrating sample magnetometer (VSM). Further analysis of the X-ray studies shows that while maintaining a pH value of 6 and 9 in a solution containing iron salts II and III ions produces ε-Fe₂O₃. Whereas a pH value of 11 produces magnetite (Fe₃O₄) phase. All of these results show that the pH has a major role in the observed phase formation of (Fe₃O₄) nanoparticles.