含二茂铁基团的芴-苯共轭化合物的合成及其性能研究

通过Suzuki偶联反应合成了二茂铁基团存在于侧链、主链和端基的苯-芴共轭化合物6、7和8,并通过 NMR和MS等表征手段对其结构进行了确认.共轭化合物中的二茂铁基团通过分子内的光致电子转移过程使6、7和8在溶液状态下的荧光猝灭.当向其溶液中加入氧化剂KMnO₄后,溶液的荧光强度显著增强,最大可增至75倍.荧光增强的幅度、对氧化剂的响应时间等性质受二茂铁在共轭化合物中的位置以及个数的影响.实验结果表明, 分子中含有一个二茂铁基团其荧光增强是线型增长的,响应时间也较短;当共轭分子中含有两个二茂铁基团时,其荧光强度的增长成二次函数关系,且其响应时间也较长.      

二茂铁表面活性剂的电化学行为

以循环伏安法为主要手段,研究了具有可逆特性的二茂铁表面活性剂(N,N-二甲基二茂铁甲基十四烷基溴化铵,Fc14)在0.1 mol/L Na2SO4溶液中形成胶束对电化学行为的影响,并讨论了pH、扫描速度及浓度对Fc14电化学行为的影响.结果表明,Fc14在pH=2左右具有良好的可逆变化特性,在氧化态(I2+)与还原态(I+)之间可实现自由转换;Fc14在玻碳电极上的logIpc~logv呈现良好的线性关系(R20.991).当Fc14的浓度大于2 mmol/L时,电化学氧化过程以扩散控制为基本特征;当浓度小于0.2 mmol/L时,电极吸附现象的特征趋于明显.与此同时,Ipc和扩散系数(D)在Fc14的临界胶束浓度(CMC)附近出现突变,这与Fc14表面张力变化趋势相吻合.     

Fluorescent and Electrochemical Sensing of Polyphosphate Nucleotides by Ferrocene Functionalised with Two ZnII(TACN)(pyrene) Complexes

The [Fc? bis{Zn^II(TACN)(Py)}] complex, comprising two Zn^II(TACN) ligands (Fc=ferrocene; Py=pyrene; TACN=1,4,7‐triazacyclononane) bearing fluorescent pyrene chromophores linked by an electrochemically active ferrocene molecule has been synthesised in high yield through a multistep procedure. In the absence of the polyphosphate guest molecules, very weak excimer emission was observed, indicating that the two pyrene‐bearing Zn^II(TACN) units are arranged in a trans‐like configuration with respect to the ferrocene bridging unit. Binding of a variety of polyphosphate anionic guests (PPi and nucleotides di‐ and triphosphate) promotes the interaction between pyrene units and results in an enhancement in excimer emission. Investigations of phosphate binding by ³¹P NMR spectroscopy, fluorescence and electrochemical techniques confirmed a 1:1 stoichiometry for the binding of PPi and nucleotide polyphosphate anions to the bis(Zn^II(TACN)) moiety of [Fc? bis{Zn^II(TACN)(Py)}] and indicated that binding induces a trans to cis configuration rearrangement of the bis(Zn^II(TACN)) complexes that is responsible for the enhancement of the pyrene excimer emission. Pyrophosphate was concluded to have the strongest affinity to [Fc? bis{Zn^II(TACN)(Py)}] among the anions tested based on a six‐fold fluorescence enhancement and 0.1 V negative shift in the potential of the ferrocene/ferrocenium couple. The binding constant for a variety of polyphosphate anions was determined from the change in the intensity of pyrene excimer emission with polyphosphate concentration, measured at 475 nm in CH₃CN/Tris‐HCl (1:9) buffer solution (10.0 mM , pH 7.4). These measurements confirmed that pyrophosphate binds more strongly (K_b=(4.45±0.41)×10⁶ M ^?1) than the other nucleotide di‐ and triphosphates (K_b=1–50×10⁵ M ^?1) tested.     

含二茂铁的β-内酰胺的研究进展

β-内酰胺类抗生素是目前最具应用价值的抗生素, 其结构特征具有β-内酰胺环的基元结构, 该类化合物的设计、合成和立体化学研究一直是有机合成化学研究的前沿和热点领域. 二茂铁凭借其独特的结构和多样的性质, 在生物和医药方面均有广泛的应用价值. 因此, 二茂铁修饰的β-内酰胺是一类结构新颖且具有潜在生物活性的化合物. 对该类化合物的深入研究, 将对新型抗生素的研发提供重要的指导意义. 综述了近年来青霉烷类和头孢烯类β-内酰胺及单环类β-内酰胺这两大类含二茂铁取代的β-内酰胺衍生物的合成与生物活性的研究进展.     

采用铁基催化剂在V型热解火焰中合成碳纳米管的实验研究

催化剂的选取对于V型热解火焰合成碳纳米管具有重要的影响.实验中分别采用五羰基铁、二茂铁、纳米铁粉等作为催化剂,取样时间为10 min,温度约为1150 K,催化剂的引入方式为喷雾热解方法,利用扫描电镜和透射电镜对合成的碳纳米管进行形态和结构表征分析.实验结果表明:利用V型热解火焰合成碳纳米管时的关键物质是纳米氧化铁颗粒...     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

Preparation of planar‐chiral multidonor phosphanylferrocene carboxamides and their application as ligands for palladium‐catalysed asymmetric allylic alkylation

Amide coupling of (S_p)‐2‐(diphenylphosphanyl)ferrocene‐1‐carboxylic acid with appropriate terminal amines mediated by 1‐hydroxybenzotriazole and a carbodiimide affords multi‐donor amides terminally functionalized with planar‐chiral (S_p)‐2‐(diphenylphosphanyl)ferrocen‐1‐yl moieties in good to excellent yields. Palladium catalysts based on these ligands efficiently promote asymmetric allylic alkylation of 1,3‐diphenylallyl acetate with in situ generated dimethyl malonate anion to give the C‐alkylated product with ees up to 93% at room temperature. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis,characterization, electrochemistry and evaluation of biological activities of some ferrocenyl Schiff bases

Synthesis of ferrocenyl Schiff bases ( 1–6 ) was carried out by the condensation reaction of 4‐ferrocenyl aniline with different substituted aromatic aldehydes and acetyl acetone. Compounds were characterized by physical measurements, elemental analysis, FT‐IR, ¹H‐NMR and ¹³C‐NMR spectroscopy. Single crystal X‐ray analysis of compound 2 showed the co‐planarity of both aromatic rings connected by a C–N double bond. Compounds demonstrated reversible one‐electron redox behavior and their peak currents were found to increase linearly with the square root of the sweep rate ν^1/2. The overall electrode processes were found to be diffusion controlled. Compounds 1 and 4 showed low cytotoxicity and appreciable antifungal, antioxidant and DNA protection activities. Copyright © 2010 John Wiley & Sons, Ltd.     

Ferrocene‐modified thiopyrimidines: synthesis,enantiomeric resolution,antitumor activity

Ferrocenylalkyl thiopyrimidines ( 6a–d to 9a–d ) were prepared via the reaction of the α‐(hydroxy)alkyl ferrocenes, FcCHR(OH) ( 1a–d ; Fc = ferrocenyl; R = H, Me, Et, Ph), with 2‐thiopyrimidines ( 2 – 5 ) in acetone at room temperature in the presence of TFA, yielding 50–95%. The resulting enantiomers were resolved using HPLC on modified cellulose as chiral selector. The antitumor activities of S‐ferrocenylethyl 2‐thiopyrimidine ( 6b ) against two murine solid tumor models, carcinoma 755 (Ca755) and Lewis lung carcinoma (LLC) were evaluated in vivo. The strong antitumor effect of compound 6b on Ca755 and LLC was demonstrated. The index of tumor growth inhibition on Ca755 equaled 95% in comparison with control. Copyright © 2010 John Wiley & Sons, Ltd.     

Molecule-Based Artificial Photosynthesis

Guidelines for the design of molecules with a long lifetime of the charge-separated state and for the formation of a self-assembled monolayer were studied by preparing various model compounds linking donor and acceptor with chemical bonds. Based on the obtained results we designed and prepared the SAMs of C₆₀-(porphyrin)-(ferrocene)-(CH₂)₁₁SH on a gold surface and observed a photocurrent with high efficiency (25% quantum yield). In addition, a well-defined, rigid-sheet-structured oligoporphyrin with 21 porphyrin chromophores was prepared as a model for antenna chlorophylls.