聚苯胺及其伪装应用研究进展

导电高分子聚苯胺(PANI)因其独特的掺杂机制和多样化的结构特征,而表现出一系列特殊的光、电等物理性能;PANI容易与其他有机或无机材料复合的特点,使它的功能与用途更加丰富广泛。因此,PANI一直是导电聚合物研究的热点。本文综述了近些年国内外关于PANI的合成、性能表征及其改性等方面的研究进展;随后重点分析了PANI在可见光、红外、雷达波等频段特性研究;最后,展望了PANI通过在分子结构设计、纳米材料复合、器件结构等方面研究及改进,解决实用中柔韧性、兼容性、寿命、功耗等方面难题,将会在光学自适应伪装、多频段复合隐身伪装等智能伪装领域发挥重要作用。     

Immobilization of the urease on eggshell membrane and its application in biosensor

Eggshell membrane is a natural material, essentially made up of protein fibers having flexibility in the aqueous solution and possessing gas and water permeability. It is used as a biomembrane for immobilization of urease for the development of a potentiometric urea biosensor. Eggshell membrane was treated with polyethyleneimine (PEI) to impart polycation characteristics. Urease was immobilized on the PEI treated eggshell membrane through adsorption. SEM study was carried out to observe the changes in surface morphology after immobilization. FTIR study of membrane was carried out to observe the changes in IR spectra after immobilization of enzyme. Immobilized membrane was associated with ammonium ion selective electrode. Biosensor exhibited sigmoidal responses for the urea concentration range from 0.5 to 10 mM. The response time of the biosensor was 120 s. A single membrane was reused for 270 reactions without loss of activity. The urease–eggshell membranes were stable for 2 months when stored in buffer even at room temperature.     

Monoparticulate films of polyaniline

Monoparticulate films were prepared from colloidal polyaniline (PANI) via the Langmuir-Blodgett (LB) technique. An aqueous dispersion of PANI obtained by aniline polymerization in the presence of polyvinyl alcohol was spread at the air-water interface in a LB trough. The floating films were transferred by the vertical lifting method to Si wafer or glass substrates. The films were very stable and could not be removed during immersion in aqueous solutions for at least several months. The color of dry monoparticulate PANI films was violet independently of the color adapted upon immersion in aqueous media at different pH. We suggest that not only the wavelength of the absorbed light, but also that of the scattered light, has an effect on the color of PANI.     

聚苯胺纳米纤维的合成及其在生物传感器中的应用

采用三嵌段共聚物P123(EO20PO70EO20)合成聚苯胺纳米纤维。利用粉末X射线衍射、透射电子显微镜、扫描电子显微镜、紫外光谱、红外光谱、热重分析等手段对产品的形态、组成和光学性质进行了表征。另外,将聚苯胺固定到玻碳电极表面构建了生物传感器。聚苯胺修饰电极对抗坏血酸的氧化显示了高的催化活性。讨论了聚苯胺纳米纤维可能的形成机理。     

Effect of iodine solutions on polyaniline films

Polyaniline (PANI) emeraldine-base films have been exposed to iodine solutions. The interaction between the films and the iodine solution was studied using the quartz-crystal microbalance (QCM) technique and the UV-visible absorption spectroscopy. The iodine-treated film of emeraldine base was subjected to dedoping process using 0.1 M ammonia solution. The resulting film was exposed again to the previously used iodine solution. Iodine was found to play multiple roles: the ring-iodination of PANI film, the oxidation of PANI to pernigraniline base, and iodine doping to PANI salt. A sensor based on PANI-coated electrode of QCM was developed to monitor the presence of iodine in solution.     

Immunophenotyping of acute leukemia using an integrated piezoelectric immunosensor array

Immunophenotyping evaluation is of particular importance for the clinical diagnosis, therapy, and prognosis of acute leukemia. In this paper, an integrated piezoelectric immunosensor array has been developed for the first time to detect the differentiated leukocyte antigens for immunophenotyping of acute leukemia. The probes (crystals) of the array were fabricated with plasma-polymerized n-butylamine film and nanometer-sized gold particles on which the Fab'-SH fragments obtained by the reduction of leukemic lineage-associated monoclonal antibodies (markers) were subsequently immobilized. Investigation results showed that the developed immunosensor array could rapidly identify normal cells from leukemic blasts and define the leukemic blasts within certain phenotypic groups (lineages) by only one analysis of the sample purified or unpurified. It permits the detection of unpurified leukocytes in the dynamic concentration range of 2 orders of magnitude (10(4)-10(6) cells mL(-1)). Up to 17 successive assay cycles with retentive sensitivity were achieved for the probes regenerated with 8 M urea. Moreover, the piezoelectric immunoassay system was applied to evaluate a number of practical specimens with immunophenotyping results in acceptable agreement with those clinically classified. The newly proposed multiparameter analysis technique provides a rapid, simple, and direct alternative tool for clinical immunophenotyping of acute leukemia.     

Thin polyaniline and polyaniline/carbon nanocomposite films for gas sensing

We have studied the gas sensing properties of five polyaniline-based materials—thick and thin PANI films, nanocomposite PANI/MWNT and PANI/SWNT films, and PANI nanogranules embedded in a polyvinylpyrrolidone matrix. The films (except for the latter) were deposited within the induction period of the polymerization process on gold interdigitated micro electrodes. Their sensitivity to NH₃, H₂, ethanol, methanol, and acetone was measured. The thin PANI film (~ 100 nm thick) prepared by a lift-off process had the sensitivity to ammonia below 0.5 ppm, which was higher than that of nanocomposite films. Two materials—thick PANI film and nanocomposite PANI/MWNT film—exhibited a shallow minimum in the temperature dependence of resistance (at 313 K and 319 K), which is a feature exploitable in practical applications, since the gas sensors should be insensitive to small temperature fluctuations at these temperatures.     

Preparation and characterization of doped polyaniline films

Stable monolayer of the polyaniline doped with camphor sulfonic acid at the air-water interface has been obtained, of which multilayers have been successfully deposited by Langmuir–Blodgett technique onto CaF₂ substrate. The limiting mean molecular area and collapse pressure are found to be 0.294 nm² and 41 mN/m, respectively. The multilayers were characterized by IR and UV-Vis-NIR spectroscopies. X-ray small-angle diffraction data show that the multilayer was periodic layer structure with the layer spacing of 1.60 nm. The comparisons are also made with characterization of the casting film.     

A novel piezoelectric quartz micro-array immunosensor for detection of immunoglobulinE

A novel multi-channel 2 x 5 model of piezoelectric (PZ) micro-array immunosensor has been developed for quantitative detection of human immunoglobulinE (IgE) in serum. Every crystal unit of the fabricated piezoelectric IgE micro-array immunosensor can oscillate without interfering each other. A multi-channel 2 x 5 model micro-array immunosensor as compared with the traditional one-channel immunosensor can provide eight times higher detection speeds for IgE assay. The anti-IgE antibody is deposited on the gold electrode's surface of 10 MHz AT-cut quartz crystals by SPA (staphylococcal protein A), and serves as an antibody recognizing layer. The highly ordered antibody monolayers ensure well-controlled surface structure and offer many advantages to the performance of the sensor. The uniform amount of antibody monolayer coated by the SPA is good, and non-specific reaction caused by other immunoglobulin in sample is found. The fabricated PZ immunosensor can be used for human IgE determination in the range of 5-300 IU/ml with high precision (CV is 4%). 50 human serum samples were detected by the micro-array immunosensor, and the results agreed well with those given by the commercially ELISA test kits. The correlation coefficient is 0.94 between ELISA and PZ immunosensor. After regeneration with NaOH the coated immunosensor can be reused 6 times without appreciable loss of activity.     

Regulation of anti-LDL immobilization on self-assembled protein G layer using CHAPS and its application to immunosensor

In antibody-based immunoassay, it is important to fabricate a structured base plate with high activity for antibody immobilization. To prevent the reduction of anti-LDL binding capacity due to protein G aggregation, detergent was introduced to control the size of protein G aggregate. The self-assembled monolayer of 11-mercaptoundecanoic acid (11-(MUA)) and hexanethiol mixture was fabricated to form the stable protein G layer. 3-[(cholamidopropyl)dimethyl-ammonio]-1-propane sulfonate (CHAPS) was used for the regulation of protein G aggregate immobilized on the 11-(MUA) surface. The effect of various CHAPS concentrations on the amount of anti-low density lipoprotein (LDL) immobilized on protein G layer was investigated. Twelve millimolars of CHAPS were determined as the optimal concentration to maximize the binding capacity of anti-LDL due to the control of protein G density on the surface. The anti-LDL layer on self-assembled protein G using CHAPS was applied to surface plasmon resonance immunosensor for detection of LDL and its detection limit was 100 pM.     

Immobilization of ibuprofen-containing nanospheres in layer-by-layer films

Liposomes have been applied to many fields as nanocarriers, especially in drug delivery as active molecules may be entrapped either in their aqueous interior or onto the hydrophobic surface. In this paper we describe the fabrication of layer-by-layer (LbL) films made with liposomes incorporating the anti-inflammatory ibuprofen. The liposomes were made with dipalmitoyl phosphatidyl choline (DPPC), dipalmitoyl phosphatidyl glycerol (DPPG) and palmitoyl oleoyl phosphatidyl glycerol (POPG). LbL films were assembled via alternate adsorption of the polyamidoamine dendrimer (PAMAM), generation 4, and liposomes containing ibuprofen. According to dynamic light scattering measurements, the incorporation of ibuprofen caused DPPC and DPPG liposomes to become more stable, with a decrease in diameter from 140 to 74 nm and 132 to 63 nm, respectively. In contrast, liposomes from POPG became less stable, with an increase in size from 110 to 160 nm after ibuprofen incorporation. These results were confirmed by atomic force microscopy images of LbL films, which showed a large tendency to rupture for POPG liposomes. Film growth was monitored using nanogravimetry and UV-Vis spectroscopy, indicating that growth stops after 10 bilayers. The release of ibuprofen obtained with fluorescence measurements was slower for the liposomes, with decay times of 9.2 and 8.5 h for DPPG and POPG liposomes, respectively, than for the free drug with a decay time of 5.2 h. Ibuprofen could also be released from the LbL films made with DPPG and POPG liposomes, which is promising for further uses in patches.     

Electrical strength of thin polyaniline films

The electrical strength of in-situ polymerized polyaniline films converted to non-conducting polyaniline base has been compared with the strength of solution-cast polystyrene and poly(methyl methacrylate) films of sub-micrometre thickness. The electrical lifetime of polyaniline film exponentially decreases with the growing electric-field strength. The electric-field strength at breakdown increases with increasing rate of electric field build-up. The breakdown areas in polyaniline films have been characterized by Raman spectroscopy. The possible physical mechanism of the breakdown in thin polymer films is discussed. The proposed concept is based on the steep increase of current density during the transition from the quadratic law at space-limited charge to the regime of complete saturation of traps. As a result, the Joule heat causes the degradation of polyaniline followed by the evaporation of chain fragments in the breakdown area.     

The carbonization of thin polyaniline films

Polyaniline films on silicon and ceramic supports were prepared in situ during the oxidative polymerization of aniline. The films were heated up to 500 °C in an inert nitrogen atmosphere. The changes in molecular structure during the carbonization have been studied by infrared spectroscopy and Raman scattering using 514, 633 and 785 nm laser excitation lines. The transformation from polyaniline salt to the base form has been detected above 100 °C. The conversion to nitrogen-containing carbon-like material followed above 200 °C. The molecular structure of the films produced during heating to 500 °C contains crosslinked phenazine-like and oxidized quinonoid units. The aniline oligomers deposited on the support in the early stages of aniline oxidation are stable during heating as it has been observed by resonance Raman scattering using 785 nm laser excitation line. The water contact angles changed after carbonization, and the films became more hydrophilic as carbonization progressed.     

Lead-free piezoelectric ceramics and thin films

Recent progress in lead-free piezoelectric ceramics and thin films with special emphasis on alkaline niobatebased and bismuth sodium titanate-based systems is reviewed concisely. Modifications of potassium sodium niobate (KNN) ceramics are presented and subsequent improvements in the electrical properties are summarized. Special attention is devoted to the phase diagram of the KNN system when a solid solution is formed with other perovskite niobates and titanates. Impact of A-site and B-site dopants on the electromechanical properties of KNN ceramics are distinguished in view of transition temperatures. It is shown that the addition of most A-site and B-site dopants reduces the transition temperatures and improves the piezoactivity at room temperature. This is attributed to the shift of polymorphic transition from tetragonal to orthorhombic phase in the vicinity of room temperature. In contrast, formation of a solid solution of KNN with 18 mol% AgNbO? revealed a significant enhancement of properties without a notable change in the transition temperatures. Also, a bismuth sodium titanate (BNT) composition is introduced with particular emphasis on its binary and ternary derivatives. Moderate piezoelectric properties reported at the morphotropic phase boundaries, formed in BNT-based solid solutions are also represented. Advances on thin films based on these two compositions are evaluated and challenges involved with development of stoichiometric thin films with low leakage current are discussed.     

聚苯胺复合材料的研究进展及其应用

复合改性技术能够有力的优化聚苯胺的性能,提高聚苯胺材料实际应用的价值.综述了聚苯胺/无机复合材料、聚苯胺/聚合物复合材料的研究进展,针对聚苯胺复合材料在金属防腐、传感器、电磁屏蔽等领域的应用情况进行了介绍.     

无铅压电陶瓷薄膜的制备及应用研究

无铅压电陶瓷的制备和应用是过去10年左右国际上研究的热点之一.近年来,由于无铅压电陶瓷薄膜可望在信息、传感、航空、机械、生物、医学等行业获得广泛应用,这类薄膜的制备和应用研究也已引起国际上的关注,并推动着无铅压电陶瓷薄膜材料和制备技术的不断发展.结合作者的研究工作,概括介绍了无铅压电陶瓷薄膜材料的研究进展,包括主要的无铅压电陶瓷薄膜材料;这类薄膜的主要制备方法,特别是射频磁控溅射法、脉冲激光沉积法和溶胶-凝胶法;以及无铅压电陶瓷薄膜材料可能的器件应用.     

Layer-by-layer nanostructured hybrid films of polyaniline and vanadium oxide

Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (ELBL) technique. Strong ionic interactions and H-bonding impart unique features to the ELBL films, which are distinct from cast films obtained with the same materials. The interactions were manifested in UV-vis and Fourier transform infrared spectroscopy data. They are enhanced by the intimate contact between the components, as the films are molecularly thin, with 25 A per PANI/V2O5 bilayer.