A study on properties and morphological structure of ferrocene-filled PVC

The crystallization, special interaction, rheological behavior, and mechanical properties of PVC/ferrocene blends were studied through WAXD, FTIR, XPS, capillary rheometry, and mechanical property tests. The experimental results showed that the tensile strength of PVC/ferrocene (100/10) amounts to 82 MPa, 1.3 times as high as that of PVC. In the presence of a small amount of ferrocene, the processability of PVC is also improved. Crystallization of ferrocene in the blend is inhibited. The FTIR characteristic peaks of ferrocene shift or disappear. A new peak appears in the C1s XPS spectra and the Cl (2p) XPS spectra of PVC/ferrocene blends, and most of the ferrocene in the blends cannot be extracted by solvent alcohol, indicating the existence of some intermolecular interactions between PVC and ferrocene which cause the mechanical strength of the blends to increase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2828–2834, 1999     

二茂铁的添加对酚醛树脂基球形活性炭活化特性以及孔径分布的影响

通过在酚醛树脂中添加有机金属二茂铁的方法,制备出含有大量中孔的酚醛树脂基球形活性炭（PHSAC）。结果表明,添加二茂铁有助于酚醛树脂基球形炭的均匀活化和提高其活化速率。不添加二茂铁的酚醛树脂基球形活炭是典型的微孔活性炭。而添加了二茂铁的酚醛树脂基球形活性炭不但含有微孔,而且含有3-5nm和10-90nm的中孔。     

Synthesis and characterisation of water soluble ferrocenes: Molecular tuning of redox potentials

A range of novel water-soluble alkylated ferrocene sulfonate compounds are reported. Mono- and di-sulfonation on a series of alkyl ferrocenes produced 1,1′-dimethyl ferrocene sulfonate, 1,1′-dimethyl ferrocene disulfonate, 1,1′-diethyl ferrocene sulfonate, 1,1′-diethyl ferrocene disulfonate, t-butyl ferrocene sulfonate, t-butyl ferrocene disulfonate, ethyl ferrocene sulfonate, ethyl ferrocene disulfonate, n-butyl ferrocene sulfonate and n-butyl ferrocene disulfonate. All compounds were characterized by NMR spectroscopy, UV/Vis spectroscopy and electrochemical analysis. ¹H and ¹³C NMR studies have revealed the formation of several isomers with sulfonation occurring on positions α and β to the alkyl substituent or on the unsubstituted cyclopentadienyl ring. Variation of the alkyl group allowed the isomeric pattern to be tuned such that the final products followed either electronic or steric control. Cyclic voltammetry of the resulting products showed that the redox potential of the iron centre can be easily manipulated by changing the substituents on the cyclopentadienyl rings. This result has significant implications in the future development of homogenous redox mediators for sensing applications.     

二茂铁与DNA作用的表面电化学研究

在研究碳纳米管电极上二茂铁电化学性质的基础上,应用二茂铁修饰电极和DNA修饰电极研究了二茂铁与小牛胸腺DNA的相互作用。结果表明,修饰电极上的二茂铁都呈现一对明显的氧化还原峰,二茂铁修饰电极与DNA的作用表现为氧化还原峰电流减小,与溶液中的两者作用情况类似,而DNA修饰电极与二茂铁的作用则表现为氧化还原峰电流增大。扫描电镜结果也证实了两种修饰电极上的二茂铁与DNA间的作用。此外,还讨论了二茂铁与DNA间的作用模式。     

Electron transfer in metal-molecule-metal junction composed of self-assembled monolayers of helical peptides carrying redox-active ferrocene units

Electronic properties of three kinds of helical peptides with or without redox-active ferrocene units were investigated by using scanning tunneling microscopy under ultrahigh vacuum. The currents through the helical peptides carrying ferrocene units at the molecular terminals became significantly larger than that through a reference peptide without any ferrocene units. On the other hand, ferrocene units in the middle of the peptide chain did not affect the current-voltage characteristics. These results indicate that the ferrocene units near the metal electrode should play an important role for efficient electron transfer between the metal and the peptide molecules, which process is one of the rate-determining steps for characterizing molecular conductance in metal-molecule-metal junction.     

1,1'-不同酰基二茂铁衍生物的合成和波谱研究

以乙酰基二茂铁和相应的乙酰氯在三氯化铝存在下在 流室温条件下合成了不对称二乙酰基二茂铁衍生物; 1-乙酰基-1'-卤素取代苯甲酰基二茂铁, 除了获得预期产品以外, 当反应在 流温度下进行时, 还得到1,3-二(二茂铁基)-丁烯-2-酮-1, 用同样方法还合成了1-乙酰基-1'-棕榈酰二茂铁和1-苯甲酰-1'-棕榈酰基二茂铁.     

Electrochemical redox reaction in a silica sol-gel glass with embedded organic electrolyte

The electrochemical redox reaction of ferrocene was studied in silica sol-gel glass with embedded organic electrolyte. This material has been prepared by mixing hydrolysed tetramethylorthosilicate sol with propylene carbonate LiClO₄ solution containing ferrocene and further gelation in a form of block or film. The electrochemical behaviour of encapsulated ferrocene was studied by cyclic voltammetry, chronoamperometry, differential pulse voltammetry and impedance spectroscopy on ultramicroelectrodes. The shape of the cyclic voltammograms corresponding to the electrooxidation of ferrocene in sol-gel block is similar to that obtained in liquid electrolyte and it does not depend on gel aging. The current substantially decreases during the first few days after gelation. Later it becomes weakly dependent on aging and the apparent diffusion coefficient of ferrocene in the gel block is about half of that in liquid electrolyte. The electrooxidation of ferrocene also occurs in film of the analogous sol-gel material cast on the surface of the electrode assembly.     

Catalytic and inhibiting effects of ferrocene on the bulk radical–coordination polymerization of methyl methacrylate from the standpoint of formal kinetics

The kinetic curves and rates of bulk radical–coordination polymerization of methyl methacrylate initiated by the benzoyl peroxide–ferrocene system at 293–373 K, initial benzoyl peroxide concentrations of 10^–4–10^–1 mol/L, and a constant initial ferrocene concentration of 10^–3 mol/L have been calculated using a mathematical model in which the process is considered from the standpoint of formal kinetics. The calculations have demonstrated that, at low methyl methacrylate conversions, ferrocene catalyzes the process at any benzoyl peroxide concentration; at medium and high methyl methacrylate conversions, deficient amounts of ferrocene with respect to benzoyl catalyze the process as well, while excess ferrocene inhibits the process. The observed effect is explained by the specific ferrocene–benzoyl peroxide interaction, which, depending on the ferrocene: benzoyl peroxide ratio, either increases or decreases the concentration of radicals in the reaction mass.     

Mixed 1D-2D inorganic polymeric zinc ferrocenylphosphonate: crystal structure and electrochemical study

Needs for ferrocene immobilization on robust host structures are considerable since derivative materials may find applications in medical areas, optical devices, or catalysis. Synthesis of phosphonate functionalized ferrocene allowed its subsequent inorganic polymerization with a zinc salt. The crystallographic structure of the compound obtained, Zn(HO(3)PFc)(2).2H(2)O, shows a unique two-dimensional ferrocene arrangement anchored on a one-dimensional Zn-O-P-O-Zn backbone. The ferrocene packing in the title compound is very similar to the packing found in molecular ferrocene. The electroactivity of Zn(HO(3)PFc)(2).2H(2)O is thoroughly studied. It shows a reversible surface oxidation of ferrocene. M?ssbauer spectroscopy for the oxidized compound shows an isomer shift of IS(2b) = 0.432 mm x s(-1) and a quadrupolar splitting of QS(2b) = 0.205 mm x s(-1), which is consistent with a stable S = 1/2 ferrocenium state. The magnetic susceptibility study, M?ssbauer spectroscopy, and galvanostatic titration show that only the ferrocene moieties present at the surface of the crystallites are reversibly oxidized. This observation is reinforced by a complex impedance study showing mainly resistive behavior and conductivity measurements indicating weak, thermally assisted, conductivity. The general properties of this compound demonstrate that phosphonato functionalization may be a useful approach for all fields concerned by immobilization of ferrocene.     

萘酰亚胺及其含二茂铁二元化合物的分子间(内)三重态能量传递

近年来萘酰亚胺类化合物作为超分子体系中的功能单元逐渐引起了人们的重视,如快速响应的光开关体系[1]、生物荧光探针体系[2]、激光染料天线分子[3]等.     

Ferrocene containing polymers

Polymers with pendent ferrocene units are synthesized by radical and anionic methods. It has been demonstrated that polymer-analogous reactions are an attractive alternative to prepare those polymers. Polymers with ferrocene units in the main chain are available from interfacial condensation reaction between ferrocene-1,1′-dicarbonic acid dichloride with α, ω-diamines. Addition of ferrocene-1,1′-dithiol onto norbornadiene yields a polymer with repeating units from ferrocene disulfide and norbornene and nortricyclane end-groups. End-capping reactions of α, ω-dimercapto-telechelics with vinylferrocene yield polymers with ferrocene end-groups.     

二茂铁及其衍生物的电化学特性与结构理论研究

研究了二茂铁及其衍生物(甲酰二茂铁,乙酰二茂铁,甲醇二茂铁和乙酸二茂铁)的电化学行为,运用结构理论给出了二茂铁D5点群群轨道能级图与二茂铁衍生物的前线轨道能级图,得出在二茂铁分子结构中1e2(dx2-y2,dxy)与3a1(dz2,4s)分别属于分子前线轨道中的HOMO和LUMO。同时用密度泛函理论(DFT)在LANL2DZ基组水平上对其结构进行了全优化,得到了二茂铁及其衍生物前线最高被占轨道(HOMO)能量值,Fe原子净电荷,对其电化学行为与前线轨道能级相对大小进行了验证。     

Click chemistry inspired synthesis of ferrocene amino acids and other derivatives

This work reports the synthesis of a wide range of ferrocenyl-amino acids and other derivatives in excellent yield. Diverse amino acid containing azides were synthesized and ligated to ferrocene employing click reaction to access ferrocenyl amino acids. Chiral alcohols, esters, diols, amines containing azido group were tagged to ferrocene via click reaction to generate ferrocene derived chiral derivatives. A novel strategy for direct incorporation of ferrocene into a peptide and a new route to 1, 1′disubstituted ferrocene amino acid derivative are reported.     

π-π Interaction intercalation of layered carbon materials with metallocene

A new hybrid material consisting of ferrocene and layered carbon (LC: graphene oxide (GO) or reduced graphene oxide (RGO)) was prepared through a facile intercalation approach. The structure of ferrocene was well maintained while the strong π-π interaction between LC and ferrocene remarkably suppressed the sublimation of ferrocene and promoted ferrocene to decompose into iron nanoparticles in between layers of LC. The hybrid exhibited excellent electrochemical properties in electrocatalytic oxidation of ascorbic acid (AA).     

Miscellaneous applications of ferrocene‐based peptides/amides

This article provides a critical review of the different applications of ferrocene‐based peptides/amides in biological as well as in non‐biological systems. Ferrocene‐based peptides/amides find many applications in different fields such as materials science, medicine, organic synthesis, bio‐organometallic and biological chemistry, asymmetric catalysis, nonlinear optics, in polymer science as redox active polymers and dendrimers, in molecular recognition as biosensors and in electrochemistry). Extensive research is being done on ferrocene‐based peptides/amides but we will highlight the various applications of ferrocene‐based peptides/amides for the period 2006–2010. The main factors that govern the potential biological and non‐biological applications are an electroactive core, a conjugated linker that can act as a chromophore and lower the oxidation potential of the ferrocene part, an amino acid or peptide derivative that can interact with other molecules via hydrogen bonding or any secondary bonding, and symmetric and asymmetric substitution on the ferrocene moiety. Copyright © 2011 John Wiley & Sons, Ltd.     

漆树漆酶的催化氧化作用——Ⅳ.二茂铁及其衍生物的酶促氧化

漆酶是含铜单电子氧化酶,主要催化邻、对苯二酚(胺)类底物氧化,它对不溶于水的二茂铁(Fc-H)及其衍生物(Fc-R)的催化氧化未见报道。本文考察了漆树漆酶在磷酸缓冲液-二乙二醇丁醚(DGBE)中对Fc-H和15个Fc-R的催化氧化反应。     

Synthesis,Characterization, and Electron-Transfer Properties of Ferrocene–BODIPY–Fullerene Near-Infrared-Absorbing Triads: Are Catecholopyrrolidine-Linked Fullerenes a Good Architecture to Facilitate Electron-Transfer?

A series of covalent ferrocene–BODIPY–fullerene triads with the ferrocene groups conjugated to the BODIPY π-system and the fullerene acceptor linked at the boron hub by a common catecholpyrrolidine bridge were prepared and characterized by 1D and 2D NMR, UV/Vis, steady-state fluorescence spectroscopy, high-resolution mass spectrometry, and, for one of the derivatives, X-ray crystallography. Redox processes of the new compounds were investigated by electrochemical (CV and DPV) methods and spectroelectrochemistry. DFT calculations indicate that the HOMO in all triads was delocalized between ferrocene and BODIPY π-system, the LUMO was always fullerene-centered, and the catechol-centered occupied orbital was close in energy to the HOMO. TDDFT calculations were indicative of the low-energy, low-intensity charge-transfer bands originated from the ferrocene–BODIPY core to fullerene excitation, which explained the similarity of the UV/Vis spectra of the ferrocene–BODIPY dyads and ferrocene–BODIPY–fullerene triads. Photophysical properties of the new triads as well as reference BODIPY–fullerene and ferrocene–BODIPY dyads were investigated by pump-probe spectroscopy in the UV/Vis and NIR spectral regions following selective excitation of the BODIPY-based antenna. Initial charge transfer from the ferrocene to the BODIPY core was shown to outcompete sub-100 fs deactivation of the excited state mediated by the catechol bridge. However, no subsequent electron transfer to the fullerene acceptor was observed. The initial charge separated state relaxes by recombination with a time constant of 150–380 ps.     

漆树漆酶的催化氧化作用——Ⅳ.二茂铁及其衍生物的酶促氧化

In phosphate buffer-diethylene glycol monobutyl ether(DGBE), the oxidations of ferrocene and 15 derivatives were investigated in the presence of Rhus vernicifera laccase. The results showed that ferrocene and 11 derivatives can be oxidized. The mechanism of Laccase catalyzed oxidation of ferrocene was put forward.     

New Synthesis of Ferrocene Monocarboxylic Acid and Systematic Studies on the Preparation of Related Key‐Intermediates

An improved technique for the preparation of ferrocenecarboxaldehyde and two new methods for the synthesis of ferrocenemonocarboxylic acid from the aldehyde or from acetyl ferrocene are described. Using the aldehyde or the monocarboxylic acid as starting materials, some important ferrocene key intermediates were prepared: monochlorocarbonyl ferrocene, alkali metal and ammonium ferrocenoates, ferrocene carboxyaldehyde diethylacetal, ferrocenecarboxamide, et …, as well as a new ferrocene derivative: piperazinium diferrocenoate.     

Adamantyl ferrocene derivatives: Antioxidant abilities and effects on model lipid membranes

A series of homoannularly and heteroannularly substituted adamantyl ferrocene derivatives has been synthesized and their effects on membrane fluidity were investigated using liposomes as the membrane models. The liposome formulations of adamantyl ferrocene derivatives were characterized by using dynamic light scattering, differential scanning calorimetry and fluorescence anisotropy measurements. It was demonstrated that adamantyl ferrocene derivatives incorporated into the liposome significantly affect the structure of the lipid bilayer. The results of the study have revealed that adamantyl ferrocene derivatives, compounds 9 – 12, partition into the hydrophobic/hydrophilic interface of the membrane, causing a significant decrease in membrane fluidity. The antioxidant potential of synthesized compounds was assessed with DPPH method and it was shown that the examined compounds possess certain antioxidant activity.