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.     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

Electroanalysis of Norepinephrine at Bare Gold Electrode Pure and Modified with Gold Nanoparticles and S‐Functionalized Self‐Assembled Layers in Aqueous Solution

Gold nanoparticles (Au‐NPs), cystamine (CA) and 3,3′‐dithiodipropionic acid (DTDPA) modified gold bare electrodes were applied in voltammetric sensors for simultaneous detection of norepinephrine (NEP), ascorbic (AA) and uric (UA) acids. A linear relationship between norepinephrine concentration and current response was obtained in the range of 0.1 μM to 600 μM M with the detection limit ≤0.091 μM for the electrodes modified at 2D template and in the range of 0.1 μM to 700 μM M with the detection limit ≤0.087 μM for the electrodes modified at 3D template The results have shown that using modified electrodes it is possible to perform electrochemical analysis of norepinephrine without interference of ascorbic and uric acids, whose presence is the major limitation in norepinephrine determination at a bare gold electrode. The modified SAMs electrodes show good selectivity, sensitivity, reproducibility and high stability.     

Amphiphilic Janus Gold Nanoparticles Prepared by Interface‐Directed Self‐Assembly: Synthesis and Self‐Assembly

Materials with Janus structures are attractive for wide applications in materials science. Although extensive efforts in the synthesis of Janus particles have been reported, the synthesis of sub‐10 nm Janus nanoparticles is still challenging. Herein, the synthesis of Janus gold nanoparticles (AuNPs) based on interface‐directed self‐assembly is reported. Polystyrene (PS) colloidal particles with AuNPs on the surface were prepared by interface‐directed self‐assembly, and the colloidal particles were used as templates for the synthesis of Janus AuNPs. To prepare colloidal particles, thiol‐terminated polystyrene (PS‐SH) was dissolved in toluene and citrate‐stabilized AuNPs were dispersed in aqueous solution. Upon mixing the two solutions, PS‐SH chains were grafted to the surface of AuNPs and amphiphilic AuNPs were formed at the liquid–liquid interface. PS colloidal particles decorated with AuNPs on the surfaces were prepared by adding the emulsion to excess methanol. On the surface, AuNPs were partially embedded in the colloidal particles. The outer regions of the AuNPs were exposed to the solution and were functionalized through the grafting of atom‐transfer radical polymerization (ATRP) initiator. Poly[2‐(dimethamino)ethyl methacrylate] (PDMAEMA) on AuNPs were prepared by surface‐initiated ATRP. After centrifugation and dissolving the colloidal particles in tetrahydrofuran (THF), Janus AuNPs with PS and PDMAEMA on two hemispheres were obtained. In acidic pH, Janus AuNPs are amphiphilic and are able to emulsify oil droplets in water; in basic pH, the Janus AuNPs are hydrophobic. In mixtures of THF/methanol at a volume ratio of 1:5, the Janus AuNPs self‐assemble into bilayer structures with collapsed PS in the interiors and solvated PDMAEMA at the exteriors of the structures.     

Novel Photoactive Polymeric Multilayer Films Formed via Electrostatic Self‐Assembly

Summary: We demonstrate a novel approach for constructing photoactive multilayer films in which the aggregation of fluorescing molecules is effectively eliminated. In the films formed via a layer‐by‐layer electrostatic self‐assembly technique, the core‐shell amphiphilic copolymer, poly[(sodium 4‐styrenesulfonate)‐block‐vinylnaphthalene], was deposited. The isolated cores served as nanosized host sites for photoactive guest molecules (pyrene, perylene). The efficient energy transfer between polymeric chromophores and perylene molecules was observed.

AFM image of a nanostructured polymeric film prepared via a layer‐by‐layer technique and containing photoactive block copolymer poly[(sodium 4‐styrenesulfonate)‐block‐vinylnaphthalene]. Below is the representative height profile taken along the drawn line.     

Electroanalysis of Norepinephrine at Bare Gold Electrode Pure and Modified with Gold Nanoparticles and S‐Functionalized Self‐Assembled Layers in Aqueous Solution. Part II

Gold electrodes modified with S‐containing compounds and gold were used for determination of norepinephrine (NEP) in aqueous solution. A linear relationship between norepinephrine concentration and current response was obtained in the range of 0.1 µM to 600 µM with the detection limit ≤0.090 µM for the electrodes modified at 2D template and in the range of 0.1 µM to 700 µM with the detection limit ≤0.075 µM for the electrodes modified at 3D template. The results have shown that modified electrodes could clearly resolve the oxidation peaks of norepinephrine, ascorbic (AA) and uric acid (UA) with peak‐to‐peak separation enabling determination of NEP, AA and UA in the presence of each other.     

Self‐Assembly and Structure of Cobalt(II) Complexes Using Diaminodiamide Ligands

The self‐assembly of Co(II) with two diaminodiamide ligands, 4,7‐diazadecanediamide and 4,8‐diazaundecanediamide, gave two different crystals, [(C₈H₁₈N₄O₂)Co(OH)₂Co(C₈H₁₈N₄O₂)]Cl₂ ( 1 ) [Co(C₉H₂₀N₄O₂)(Cl)(H₂O)]·Cl·2H₂O ( 2 ). Structures of 1 and 2 were characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 shows a novel type of binuclear complex with distorted octahederal coordination geometry around the Co atoms through the hydroxo bridges. By using inter‐connector N‐H···N hydrogen bonding interactions as building forces, each cationic moiety [(C₈H₁₈N₄O₂)Co(OH)₂Co(C₈H₁₈N₄O₂)]²⁺ is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chain‐like structure. The chains are further connected into a 2D layer in a (4,4)‐topology via N‐H···Cl_free hydrogen‐bonding interactions. Structural data for 2 indicate that the cobalt atom adopts a six‐coordinated N₂O₄ environment, giving a distorted octahedral geometry, where two N‐ and two O‐donor sets of ligand located at equatorial positions and one water and one chloride occupied at axial positions. Through NH···Cl‐Co and OH···Cl‐Co contacts, each cationic moiety [Co(C₉H₂₀N₄O₂)(Cl)(H₂O)]⁺ in 2 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to steric strain effect of the diaminodiamide ligand.     

Self‐Assembly of Platinum Nanoparticle/Multiwalled Carbon Nanotube Multilayer Film on Au Substrate Electrode

A novel approach to assemble multilayer films of Pt nanoparticle/multiwalled carbon nanotube (MWNTs) composites on Au substrate has been developed for the purpose of improving the methanol oxidation efficiency by providing high catalytic surface area. MWNTs were firstly functionalized with 4‐mercaptobenzene and then assembled on an Au substrate electrode. Pt nanoparticles were fabricated and attached to the surface of the functionalized MWNTs subsequently. Thus a layer of Pt/MWNT composites were assembled on the Au substrate electrode. Repeating above process can assemble different layers of film of Pt/MWNTs composites on the Au electrode. Cyclic voltammetry shows that the Au electrode modified with two layers of film of Pt/MWNT composites exhibits high catalytic ability and long‐term stability for methanol oxidation. The layer‐by‐layer self‐assembly technique provides an efficient strategy to construct complex nanostructure for improving the methanol oxidation efficiency by providing high catalytic surface area.     

Layer‐by‐Layer Assembly of Polyelectrolyte and Nanoparticles,Monitored by Capillary Electrophoresis

Layer‐by‐layer (LBL) assembly is a versatile nanofabrication technique, and investigation of its kinetics is essential for understanding the assembly mechanism and optimizing the assembly procedure. In this work, the LBL assembly of polyelectrolyte and nanoparticles were monitored in situ by capillary electrophoresis (CE) for the first time. The assembly of poly(diallyldimethylammonium chloride) (PDDA), and gold nanoparticles (AuNPs) on capillary walls causes surface‐charge neutralization and resaturation, and thus yields synchronous changes in the electroosmotic flow (EOF). The EOF data show that formation of multilayers follows first‐order adsorption kinetics. On the basis of the fit results, influencing factors, including number of layers, concentration of materials, flow rate, and size of AuNPs, were investigated. The stability and robustness of the assembled coatings were also characterized by CE. It was found that degradation of PDDA layers follows first‐order chemical kinetics, while desorption of AuNPs takes place in a disorderly manner. The substrate strongly affects assembly of the underlying layer, while this effect is rapidly screened with increasing number of layers. Furthermore, we demonstrate that the EOF measuring step does not disturb LBL assembly, and the proposed method is reliable and rugged. This work not only studies in detail the LBL adsorption/desorption process of polyelectrolyte and nanoparticles, but also offers an alternative tool for monitoring multilayer buildup. It may also reveal the potential of CE in fields other than analytical separation.     

Efficient Electrocatalytic Detection of Epinephrine at Gold Electrodes Modified with Self‐Assembled Metallo‐Octacarboxyphthalocyanine Complexes

Electrocatalysis of epinephrine at gold electrode pre‐modified with the self‐assembled monolayer of cysteamine and subsequently integrated with novel metallo‐octacarboxyphthalocyanine (MOCPc where M=Fe, Co and Mn) complexes (Au‐Cys‐MOCPc) was investigated. The electrodes showed response to the presence of epinephrine. The oxidation peak potential (E_p/V vs. Ag|AgCl, sat'd KCl) and charge transfer resistance (R_ct (kΩ)) in epinephrine solution depend markedly on the central metal of the phthalocyanine cores: Au‐Cys‐FeOCPck_ch=4.1×10⁷ M^?1 s^?1) which is higher than that of the Au‐cys‐CoOCPc or Au‐cys‐MnOCPc electrode. Mechanism, recognizing the mediation of the electrocatalytic process by the central M(II)/M(III) redox processes was proposed. Epinephrine electro‐oxidation at the Au‐cys‐FeOCPc electrode was studied in more details for the response characteristics. The diffusion coefficient of epinephrine was evaluated as (2.62±0.23)×10^?9 cm² s^?1. It was established that Au‐Cys‐FeOCPc is suitable for sensitive determination of epinephrine in physiological pH (7.40) conditions showing linear concentration range of up to 300 nM, with excellent sensitivity (0.53±0.01 nA nM^?1), and very low limits of detection (13.8 nM) and quantification (45.8 nM). The peak separation between ascorbic acid and epinephrine is large enough (190 mV) to permit simultaneous determination of both epinephrine and ascorbic acid in physiological pH 7.4 conditions using the Au‐cys‐FeOCPc electrode. Au‐cys‐FeOCPc electrode was successfully used for the determination of epinephrine in epinephrine hydrochloric acid injection with recovery of ca. 98.4%.     

Vapor‐Surface Sol‐Gel Deposition of Titania Alternated with Protein Adsorption for Assembly of Electroactive,Enzyme‐Active Films

Combining vapor‐surface sol‐gel deposition of titania with alternate adsorption of oppositely charged iron heme proteins provided ultrathin {TiO₂/protein}_n films with reversible voltammetry extended to 15 TiO₂/protein bilayers, more than twice that of more conventional polyion‐protein or nanoparticle‐protein films made by alternate layer‐by‐layer adsorption. Catalytic activity toward O₂, H₂O₂, and NO was also improved significantly compared to the conventionally fabricated films. The method involves vaporization of titanium butoxide into thin films of water, forming porous TiO₂ sol‐gel layers. Myoglobin (Mb), hemoglobin (Hb), and horseradish peroxidase (HRP) were assembled by adsorption alternated with the vapor‐deposited TiO₂ layers. Improved electrochemical and catalytic performance may be related to better film permeability leading to better mass transport within the films, as suggested by studies with soluble voltammetric probes, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical and electrocatalytic activity of the films can be controlled by tailoring the amount of water with which the metal alkoxide precursor vapor reacts and the number of bilayers deposited in the assembly.     

钒取代多金属氧酸盐/聚酰胺-胺多层膜的制备及其电催化性能

用层接层自组装的方法制备了过渡金属钒取代的多金属氧酸盐PMo11VO4-40/聚酰胺-胺多层纳米复合膜. X射线光电子能谱(XPS)、紫外-可见光谱(UV-Vis)、循环伏安(CV)测定和分析结果表明, PMo11VO4-40和聚酰胺-胺通过静电相互作用形成了纳米交替多层膜,且膜的增长均匀. 复合膜的循环伏安图呈现出四对氧化还原峰(一个V的单电子和三个Mo的双电子), 峰电流与扫描速率成正比, 其式量电位随着pH 的增加而线性负移, 表明电极过程属于表面控制过程, 电荷传递很快且有氢离子参与多金属氧酸盐的氧化还原反应. 该方法制备的多层膜修饰电极稳定性好, 对NO-2、BrO-3及H2O2具有良好的催化还原活性.     

Electrochemistry and Electrocatalysis of Myoglobin Loaded into Multilayer Films Assembled with Phytic Acid and Chitosan

Natural polymer polysaccharides chitosan (CS) was successfully assembled with phytic acid (PA) into {PA/CS}_n layer-by-layer films. Myoglobin (Mb) could be gradually “absorbed” or loaded into {PA/CS}_n films when the films were immersed into Mb solutions, forming {PA/CS}_n-Mb films. The {PA/CS}_n-Mb films demonstrated well-defined and quasi-reversible cyclic voltammetry (CV) responses for Mb Fe^III/Fe^II redox couple and were used to catalyze electrochemical reduction of oxygen and hydrogen peroxide. The interaction between Mb and {PA/CS}_n films was explored and discussed, which suggested that the electrostatic attraction might play a major role in loading Mb into the films. This new kind of film incorporated with redox proteins could be used to fabricate the new type of biosensors or bioreactors without using mediators.     

Tunable Metal‐Enhanced Fluorescence by Stimuli‐Responsive Polyelectrolyte Interlayer Films

In this paper, we report on the tunable metal‐enhanced fluorescence (MEF) of Ag nanostructures. Because of the good MEF properties of the highly dendritic Ag nanostructures, we obtained an increase of up to 25 times for the weak fluorescence of porphyrin molecules (Por^4–). More importantly, by the introduction of a stimulus‐responsive PAA/PDDA multilayer film as an interlayer, the distance between the fluorophores and the Ag nanostructures could be tuned by immersing the substrates into solutions of different ionic strength or pH. The MEF behavior of the composite films could thus be tuned in a controlled manner, because of the distance dependent nature of the MEF effects.

     

A Non‐Enzymatic Hydrogen Peroxide Sensor Based on Gold Nanoparticles/Carbon Nanotube/Self‐Doped Polyaniline Hollow Spheres

In this study, a novel non‐enzymatic hydrogen peroxide (H₂O₂) sensor was fabricated based on gold nanoparticles/carbon nanotube/self‐doped polyaniline (AuNPs/CNTs/SPAN) hollow spheres modified glassy carbon electrode (GCE). SPAN was in‐site polymerized on the surface of SiO₂ template, then AuNPs and CNTs were decorated by electrostatic absorption via poly(diallyldimethylammonium chloride). After the SiO₂ cores were removed, hollow AuNPs/CNTs/SPAN spheres were obtained and characterized by transmission electron microscopy (TEM), field‐emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). The electrochemical catalytic performance of the hollow AuNPs/CNTs/SPAN/GCE for H₂O₂ detection was evaluated by cyclic voltammetry (CV) and chronoamperometry. Using chronoamperometric method at a constant potential of ?0.1 V (vs. SCE), the H₂O₂ sensor displays two linear ranges: one from 5 µM to 0.225 mM with a sensitivity of 499.82 µA mM^?1 cm^?2; another from 0.225 mM to 8.825 mM with a sensitivity of 152.29 µA mM^?1 cm^?2. The detection limit was estimated as 0.4 µM (signal‐to‐noise ratio of 3). The hollow AuNPs/CNTs/SPAN/GCE also demonstrated excellent stability and selectivity against interferences from other electroactive species. The sensor was further applied to determine H₂O₂ in disinfectant real samples.     

Self‐Assembled Redox System for Bioelectrocatalytic Assay of L‐Ascorbylphosphate and Alkaline Phosphatase Activity

Ferrocene‐terminated self‐assembled monolayer (Fc‐SAM) on gold was used as an electron‐transfer mediator in the electrochemical assay of L ‐ascorbic acid 2‐phosphate (AAP). The assay is based on the enzymatic action of alkaline phosphatase (ALP), which triggers the release of vitamin C (L ‐ascorbic acid, AA) from AAP. The latter is easily oxidized on the Fc‐SAM under the diffusion limiting conditions that favors quantitative measurement of the AA concentration on a rotating disk electrode. We demonstrate the utility of the electrochemically active Fc‐SAM to probe the mechanism and to determine the kinetic parameters of an enzymatic reaction. The electrochemical technique was compared to a conventional spectrophotometric method of ALP activity detection using p‐nitrophenylphosphate (p‐NPP) as a substrate. We demonstrate that our new technique is also suitable for the analytical determination of ALP activity. The detection limits for both AAP and ALP were found to be 13 μM and 2 pM, respectively.