二茂铁标记DNA电化学探针的研制及性质研究

以乙基－（3－二甲基丙基）碳化二亚胺盐酸(EDC)为偶联活化剂,利用缩合反应分别将电化学活性物质氨基二茂铁（Aminoferrocene,AFC)和苯基二茂铁（Ferrocencearboxadehyde,FCA)成功地标记在变性小牛胸腺DNBA片段上,制备成二茂铁标记DNA探针,分别采用电化学,紫外,红外光谱等方法研究了二茂铁标记DAN探针的性质,计算了二茂铁的标记效率,变性小牛胸腺DNA的反应效率以及二茂铁化合物与变性小牛胸腺DNA的反应比率,实验表明,氨基二茂铁和醛基二茂铁与DNA上的磷酸基是以1：1比率进行的反应,该标记反应不影响DNA链碱基的紫外吸收,二茂铁标记DNA探针在石墨电极上有良好的电化学影响,将制备好的二茂铁标记DNA电化学探置于冰箱中冷冻（温度低于－15度）保存3个月后用于测定,峰电流仅下降1．2％。     

A Novel Electrochemical Immunosensor for Prostate-Specific Antigen Based on Noncovalent Nanocomposite of Ferrocene Monocarboxylic Acid with Graphene Oxide

A novel electrochemical immunosensor was developed for the determination of prostate-specific antigen based on immobilization of appropriate antibodies on gold nanoparticles and a poly-(2,6-pyridinediamine) modified electrode. The nanocomposite of ferrocene monocarboxylic acid hybridized graphene oxide was prepared by a π-π stacking interaction and was used as the electrochemical probe. A sandwich-type complex immunoassay was applied with polyclonal prostate-specific antigen antibodies labeled with the nanocomposite of ferrocene monocarboxylic acid hybridized graphene oxide. In order to improve the sensitivity, a potentiostatic method was used to reduce graphene oxide. Cyclic voltammetry and differential pulse voltammetry were employed to characterize the assembly process and the performance of the immunosensor. Under optimal conditions, the peak current of the immunosensor increased with concentration, showing a linear relationship between the peak current and the logarithm of the prostate-specific antigen concentrations in a wide range of 2.0 pg mL^?1 to 10.0 ng mL^?1 with a low detection limit of 0.5 pg mL^?1. The immunosensor was used for the determination of prostate-specific antigen in serum.     

N-二茂铁酰胺酸的合成及反应研究

有机化学中胺与酸酐的反应已有详细、广泛地研究,但在金属有机化学中有关氨基茂金属与酸酐的酰化反应却未见文献报道.为模拟具有生物活性的含有酰胺结构的一类新型金属有机化合物,研究氨基二茂铁与酸酐反应的条件,我们使氨基二茂铁与环二酸酐反应,合成并表征了7种N-二茂铁酰胺酸(A-G),考查它们与金属离子的螯合作用并分离出螯合物H和I.这些配合物(A-I)和酸酐K均未见文献报道.     

Stille Cross‐Coupling of a Racemic Planar‐Chiral Ferrocene and Crystallographic Trace Analysis of Catalysis Intermediates and By‐products

A pressure‐controlled procedure for the S_N1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd⁰‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ).     

A New Route to Vitamin E Key‐Intermediates by Olefin Cross‐Metathesis

Ru‐Catalyzed olefin cross‐metathesis (CM) has been successfully applied to the synthesis of several phytyl derivatives ( 2b, 2d – f, 3b ) with a trisubstituted C?C bond, as useful intermediates for an alternative route to α‐tocopheryl acetate (vitamin E acetate; 1b ) (Scheme 1). Using the second‐generation Grubbs catalyst RuCl₂(C₂₁H₂₆N₂)(CHPh)PCy₃ (Cy = cyclohexyl; 4a ) and Hoveyda–Grubbs catalyst RuCl₂(C₂₁H₂₆N₂){CH‐C₆H₄(O‐ⁱPr)‐2} ( 4b ), the reactions were performed with various C‐allyl ( 5a – f, 7a,b ) and O‐allyl ( 8a – d ) derivatives of trimethylhydroquinone‐1‐acetate as substrates. 2,6,10,14‐Tetramethylpentadec‐1‐ene ( 6a ) and derivatives 6c – e of phytol ( 6b ) as well as phytal ( 6f ) were employed as olefin partners for the CM reactions (Schemes 2 and 5). The vitamin E precursors could be prepared in up to 83% isolated yield as (E/Z)‐mixtures.     

无柔性末端链的二茂铁液晶化合物的合成、结构及取代基对介晶性的影响

合成了中心桥键为酯基和Schiff碱基连接且分子中含4个苯环的17个化合物,其中有带支链和不带支链的化合物,化合物的结构通过IR,NMR和元素分析进行表征,其介晶性通过DSC和偏光显微镜进行研究.讨论了取代基对介晶性的影响.结果表明,该类型结构的二茂铁化合物绝大多数具有液晶性,取代基对介晶性的影响较小.     

Oxidation‐induced the Formation of Vesicles from Ferrocene Derivative Superamphiphiles

The stimuli‐responsive vesicles were prepared via electrochemical oxidation on the mixture solution of ferrocenylmethyl‐trimethylammonium iodide (FcMI) and sodium deoxycholate (NaDC). The vesicle structure and morphology are characterized respectively by transmission electron microscopy (TEM), dynamic light scattering (DLS) and atomic force microscopy (AFM). The vesicle shells can be clearly observed by TEM with the thickness ranging from several to several tens of nanometers and their outer diameters at the range of 50‐200 nm. The formation of vesicular structures is also supported via AFM measurements, and the ratio of the diameter and height of the nanospheres was estimated to be ca. 10, indicating the shell collapse. The obtained results are significant for the preparation of smart supramolecular aggregates.     

Synthesis and Characterization of Ferrocene Derived Cyclic Carbaphosphazenes

Dialkylamino substituted cyclic carbaphosphazenes, (R 2 NCN) 2 (NPCl 2 ) were prepared and reacted with the ferrocene derived hydroxymethyl phosphine sulfide FcCH(CH 3 )P(S)(CH 2 OH) 2 after dilithiation to yield a series of new spirocyclic derivatives of cyclic carbaphosphazenes having ferrocenyl pendant groups. To confirm the formation of six membered spirocycles and to compare their spectral features, transesterification reactions of FcCH(CH 3 )P(S)(CH 2 OH) 2 also were carried out with P(NR 2 ) 3 , yielding the six membered heterocycles FcCH 2 P(S)(CH 2 O) 2 PNR 2 (R = Me, Et). The compounds were characterized by 1 H, 31 P, 13 C NMR, mass spectra, and elemental analysis.     

Ferrocene compounds XXIII. Synthesis and reactions of the new type of methyl ferrocyloxyalkanoates

The new types of ferrocenyloxaaliphatic acid ester, FcCHROCHR′COOMe (R = H, Me, Ph; R′ = H, Me) (7) have been prepared by the action of alkoxides derived from methyl glycolate or methyl lactate on the corresponding ferrocenylcarbinyl acetates (2) or N,N,N-trimethylferrocylammonium iodides (4). The esters obtained were accompanied by a small quantity of oligomeric esters, FcCHR(OCHR′CO)_n OMe (9), and with more or less ferrocyl methyl ethers (8). As opposed to the alkaline hydrolysis of the analogous methyl benzoxyacetate (6) into benzoxyacetic acid (5) the acidification of sodium alkanoates 10 obtained by saponification of esters 7 gave unexpectedly the corresponding ferrocenylcarbinols 1. In a similar way the esters 7 were converted into mixtures of the mentioned carbinols and diferrocyl ethers 11 under action of aqueous hydrochloric acid. The mechanisms of the reactions 10 → 1 and 7 → 1, 11 are discussed.     

A Synthesis Detour to Planar‐Diastereoisomeric Ferrocene Derivatives around an Unexpected Rearrangement of ortho‐Lithiated Kagan's Template [S(S)]‐(p‐Tolylsulfinyl)ferrocene

Usually, ortho lithiation of Kagan's template 1 and quenching with electrophiles leads highly diastereoselectively to planar‐chiral 1,2‐disubstituted ferrocenes. Surprisingly, lithiation of 1 with lithium diisopropylamide (LDA) followed by addition of paraformaldehyde afforded regioisomer (+)‐{[S(S)]‐[4‐(2‐hydroxyethyl)phenyl]sulfinyl}ferrocene ( 2 ), which was converted to (+)‐{[S(S)]‐{4‐{2‐[(methylsulfonyl)oxy]ethyl}phenyl}sulfinyl}ferrocene ( 3 ) (Scheme 1). The desired diastereoisomer (l)‐1‐(hydroxymethyl)‐2‐(p‐tolylsulfinyl)ferrocene ( 5 ) in turn could also be obtained by ortho lithiation of 1 with LDA but by quenching with DMF to yield aldehyde 4 first, which then was reduced with NaBH₄ to 5 . Finally, target compound (l)‐1‐[(dimethylamino)methyl]‐2‐(p‐tolylsulfinyl)ferrocene ( 6 ) was obtained by substitution of the OH group of 5 under mild conditions or directly by ortho lithiation of 1 with lithio‐2,4,6‐triisopropylbenzene (=2,4,6‐triisopropylphenyl)lithium; LTP) followed by quenching with N,N‐dimethylmethyleneiminium chloride. At low temperatures, reaction of 1 with LDA leads, via the preferred diastereoisomeric transition state ‘exo’‐ 7 and under extrusion of a (diisopropylamine)lithium complex of type 8 , in a highly selective manner, to diastereoisomeric ortho‐lithiated chelate (l)‐ 9 (Scheme 2). The reaction of 1 to 2 is explained by a rearrangement of (l)‐ 9 to {[S(S)] [4‐(lithiomethyl)phenyl]sulfinyl}ferrocene 10 , which is acid‐catalyzed by coordinated diisopropylamine in complexes of type 8 . This rearrangement is not observed if LTP is used as base or, in case LDA is applied, if the electrophile is sufficiently reactive at low temperatures.     

Electrochemical Analysis of D‐Penicillamine Using a Carbon Paste Electrode Modified with Ferrocene Carboxylic Acid

The electrochemical behavior of D ‐penicillamine (D ‐PA) studied at the surface of ferrocene carboxylic acid modified carbon paste electrode (FCAMCPE) in aqueous media using cyclic voltammetry and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00), the oxidation of D ‐PA at surface of such an electrode is occurred about 420 mV less positive than that an unmodified carbon paste electrode (CPE). The catalytic oxidation peak current was linearly dependent on the D ‐PA concentration and a linear calibration curve was obtained in the ranges 7.5×10^?5 M – 1.0×10^?3 M and 6.5×10^?6 M?1.0×10^?4 M of D ‐PA with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 6.04×10^?5 M and 6.15×10^?6 M. This method was also used for the determination of D ‐PA in pharmaceutical preparation (capsules) by standard addition method.     

Synthesis and Photophysical Properties of Ferrocene Containing Monomer and Polymer

Summary. Synthesis of a new monomer and polymer containing both ferrocene and hydrazone moieties are reported. The obtained materials were examined by various techniques including differential scanning calorimetry, UV, IR, NMR spectroscopy, and time of flight method. These materials may be of particular interest for the development of future electrophotographic photoreceptors as electron photoemission spectra of the layers showed ionization potentials of 5.35–5.41 eV. The hole drift mobility values in compositions of the designed structures with bisphenol Z polycarbonate exceeded 10⁻⁸ cm²/Vs at strong electric fields.     

Intermolecular Interactions in Mixed Self‐Assembled Monolayers of Ferrocene

Electrochemical characterization of mixed self‐assembled monolayers (SAMs) of 6‐ferrocenyl‐1‐hexanethiol (FcH) and mercaptoundecanoic acid tyrosinamide (MUATyr) on gold is reported. Single‐component SAMs of FcH presented repulsive intermolecular interactions (vGθ_T=?1.12), while mixed SAMs of FcH/MUATyr (1 : 1) exhibited attractive interactions (vGθ_T=+0.20), with a homogeneous distribution of both components. Electrochemical kinetic determinations on mixed SAMs of FcH/MUATyr, indicated a secondary electron transfer pathway between the redox centers of both components. Higher amounts of FcH in the mixed SAMs lowered the observed rate of electron transfer of MUATyr. The oxidation of FcH caused an anodic shift of 160 mV in the voltammetric wave of MUATyr.     

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。     

Highly Thiocyanate‐Selective PVC Membrane Electrode Based on Lipophilic Ferrocene Derivative

A novel anion‐selective PVC membrane electrode based on bis‐[(3‐ferrocenyl)‐(2‐crotonic acid)] copper(II) complex [Cu(II)‐BFCA] as neutral carrier is described, which demonstrates excellent potentiometric response characteristics toward thiocyanate ion and anti‐Hofmeister selectivity sequence in following order: SCN^?>I^?>ClO >Sal^?>Br^?>NO >Cl^?≈NO >SO >SO . The electrode shows a near‐Nernstian response for thiocyanate ion in a wide range of 9.0×10^?7–1.0×10^?1 M with a detection limit 6.8×10^?7 M and a slope of ?59.1 mV/decade in pH 5.0 of phosphate buffer solution at 20 °C. The influences of lipophilic cationic and anionic additives on the response properties of the electrode were investigated. High sensitivity and wide linear dynamic range were observed for the electrode in the presence of hexadecyltrimethylammoniumborate (HTAB) as a lipophilic cationic additive. The electrode was successfully applied to the determination of thiocyanate ion in waste water and human saliva.     

二茂铁及其胺甲基类取代衍生物的紫外光解自由基的研究

本文用自旋捕捉-ESR技术研究了二茂戊铁、环二烯和胺甲基类取代二茂铁的紫外光解过程中的活泼自由基。结果表明,二茂铁光解初级过程中生成的自由基为(C_5H_5Fe)·和C_5H_5·,其衍生物光解则生成(C_5H_5Fe)·和RC_5H_4·,而(C_5H_5Fe)·还可以进一步分解给出C_5H_5和Fe。     

Polyelectrolyte Multilayer Films Containing Ferrocene: Effects of Polyelectrolyte Type and Ferrocene Contents in the Film on the Redox Properties

Electrochemical properties of Fc‐PEM films have been studied by changing the chemical structure of the polymer chains and the content of Fc moiety in the film systematically. We have prepared a series of PEM films by a layer‐by‐layer deposition of polycations, Fc‐modified poly(allylamine) (Fc‐PAA) and poly(ethyleneimine) (Fc‐PEI), and polyanionic poly(vinyl sulfate) (PVS) on the surface of a gold electrode. The redox properties of the Fc‐PAA/PVS and Fc‐PEI/PVS films depended significantly on the content of Fc moiety in the polymer chains and on the polymer type. Fc‐ PAA and Fc‐PEI polymer chains can penetrate 3 or 4 PAA/PVS bilayers inserted between the redox polymers and electrode. The Fc‐PAA film‐modified electrode can be used for electrocatalytic oxidation of ascorbic acid.     

Synthesis,Coordination, and Spectroscopic Properties of 2,2′‐Bipyridyldimesitylpalladium(II) and 6‐Mesityl‐2,2′‐bipyridyldimesitylpalladium(II)

The synthetic route to the dimesitylpalladium(II) complex [(bpy)PdMes₂] ( 1 ) (Mes = mesityl = 2,4,6‐trimethyl phenyl) does not only give the desired compound but also the 6‐mesityl‐2,2′bipyridyldimesitylpalladium [(6‐Mes‐bpy)PdMes₂] ( 2 ) complex and the free ligand 6,6′‐dimesityl‐2,2′‐bipyridine in reasonable yields. Single crystals of 2 were examined by X‐Ray diffraction. The compound reveals a sterically crowded molecular structure. An intramolecular π‐stacking interaction was found between the mesityl substituent on the bipyridine ligand and the adjacent mesityl ligand. The electrochemical behaviour of 1 and 2 together with a related compound was examined at various temperatures showing two reversible reduction reactions and reversible one‐electron oxidation steps at low temperatures. The latter are assigned to Pd^II/Pd^III couples.     

与二茂铁酰基相连的螺噁嗪的合成、结构及性质

在二环已基碳二亚胺(DCC)存在下, 将9′-羟基螺噁嗪与二茂铁甲酸进行酯化缩合, 合成了一种与二茂铁酰基相连的螺噁嗪衍生物2, 用核磁共振氢谱、碳谱、红外光谱、高分辨质谱和X射线单晶衍射对其结构进行了表征. 化合物2在几种有机溶剂中都表现出了良好的光致变色性质; 通过实验证明了在无冰水浴冷却条件下, 用高压汞灯照射时化合物2在二氯甲烷中表现出的特殊变色性是酸致变色的结果; 同时还研究了化合物2在固体PMMA薄膜中的光致变色性质. 在高压汞灯照射下,化合物2在二氯甲烷溶液中显示了良好的荧光性. 循环伏安法测定结果表明化合物2具有良好的氧化还原可逆性.     

New Donor‐Functionalized Cp Ligands: Synthesis and Complexation Behaviour of Quinoxalyl and Benzothiadiazolyl Systems

Sodium cyclopentadienide reacts as nucleophile with 4,7‐dibromo‐2,1,3‐benzothiadiazole (BTZ) and leads to the new donor‐functionalized ligand Cp^BTZ. Related quinoxalyl Cp systems have been prepared using Pd‐catalyzed coupling with zincated Cp‐metal complexes. The new ligands comprise two N‐donor atoms; one of them is located in a distal position relative to the metal centre so that it cannotcoordinate in a chelating manner. With Cp^BTZ ligand derivatives severalmetal complexes have been synthesized. The new chromium(III) complex Cp^BTZCrCl₂ ( 12 ) becomes upon activation an active catalyst for the polymerization of ethylene. Relying on DFT calculations and analysis of spin‐density distribution combined with paramagnetic NMR data a chelating coordination of the Cp^BTZ ligand is feasible in 12 .