Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Poly(3-octylthiophene)/stearic acid langmuir and langmuir-blodgett films: preparation and characterization

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Langmuir and Langmuir-Blodgett films of a quinoline-fluorene based copolymer

The fabrication of Langmuir-Blodgett (LB) films of synthetic polymers allows the control of molecular architecture in order to optimize physical properties. In this paper, the surface chemistry of a quinoline-fluorene based copolymer spread on the air-water interface is investigated. Surface pressure-area isotherms as well as Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) were employed to characterize the films, which could be transferred to solid supports by the LB technique. Atomic force microscopy as well as UV-Vis and fluorescence spectroscopies have shown a regular deposition of the polymers, and the luminescence properties could be controlled with the number of layers deposited on the solid support. As a result, the photoluminescence of the LB films was considerably higher than that observed for the spin coated film, and the maximum emission peak was shifted to higher energies, which is attributed to the molecular-level interactions within the layer-ordered structure of the LB film. The luminescence response would possibly be tuned to approach the highest level, which allows the films to be employed in future applications in efficient optical devices such as organic light-emitting diodes (OLEDs). (C) 2011 Elsevier B.V. All rights reserved.

Immbolization of uricase enzyme in Langmuir and Langmuir-Blodgett films of fatty acids: Possible use as a uric acid sensor

Preserving the enzyme structure in solid films is key for producing various bioelectronic devices, including biosensors, which has normally been performed with nanostructured films that allow for control of molecular architectures. In this paper, we investigate the adsorption of uricase onto Langmuir monolayers of stearic acid (SA), and their transfer to solid supports as Langmuir Blodgett (LB) films. Structuring of the enzyme in beta-sheets was preserved in the form of 1-layer LB film, which was corroborated with a higher catalytic activity than for other uricase-containing LB film architectures where the beta-sheets structuring was not preserved. The optimized architecture was also used to detect uric acid within a range covering typical concentrations in the human blood. The approach presented here not only allows for an optimized catalytic activity toward uric acid but also permits one to explain why some film architectures exhibit a superior performance. (C) 2011 Elsevier Inc. All rights reserved.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with twomonoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LBmethod may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.

Structure and thermal stability of Langmuir-Blodgett films of barium arachidate

The structures of multilayer Langmuir-Blodgett films of barium arachidate before and after heat treatment have been investigated using both atomic force microscopy (AFM) and grazing incidence synchrotron X-ray diffraction (GIXD). AFM gave information on surface morphology at molecular resolution while GIXD provided quantitative details of the lattice structures of the films with their crystal symmetries and lattice constants. As-prepared films contained three coexisting structures: two triclinic structures with the molecularchains tilted by about 20degrees from the film normal and with 3 x 1 or 2 x 2 super-lattice features arising from height modulation of the molecules in the films; a rectangular structure with molecules perpendicular to the film surface. Of these, the 3 x 1 structure is dominant with a loose correlation between the bilayers. In the film plane both superstructures are commensurate with the local structures, having different oblique symmetries. The lattice constants for the 3 x 1 structure are a(s) = 3a = 13.86 Angstrom, b(s) = b = 4.31 Angstrom and gamma(s) = gamma = 82.7degrees; for the 2 x 2 structure a(s) = 2a = 16.54 Angstrom, b(s) = 2b = 9.67 Angstrom, gamma(s) = gamma = 88degrees. For the rectangular structure the lattice constants are a = 7.39 Angstrom, b = 4.96 Angstrom and gamma = 90degrees. After annealing, the 2 x 2 and rectangular structures were not observed, while the 3 x 1 structure had developed over the entire film. For the annealed films the correlation length in the film plane is about twice that in the unheated films, and in the out-of-plane direction covers two bilayers. The above lattice parameters, determined by GIXD, differed significantly from the values obtained by AFM, due possibly to distortion of the films by the scanning action of the AFM tip. (C) 2004 Published by Elsevier B.V.

The structure of ultrathin Langmuir-Blodgett films of cadmium behenate

Grazing incidence x-ray-diffraction investigations of the structures of Langmuir-Blodgett films of cadmium behenate with 1, 2, 3, 5, and 21 monolayers are reported. The single monolayer film, deposited on a hydrophilic substrate, showed a hexagonal structure, whereas the bilayer film, deposited on a hydrophobic substrate, had a rectangular structure with herringbone orientation of the acyl chains. With multilayer films formed on a hydrophilic substrate, it was possible to detect that the hexagonal structure of the first layer was retained when additional layers were deposited and that the additional layers had the same rectangular structure as the bilayer. (c) 2005 American Institute of Physics.

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine,hereafter named tetrapyridyl porphyrins with distinct central ions (2H(+), Zn(2+), Cu(2+), Ni(2+)). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl(3) solutions. The shift was larger for the non-substituted H(2)TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with on further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H(2)TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H(2)TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups. (C) 2008 Elsevier B.V. All rights reserved.

Langmuir and Langmuir-Blodgett (LB) films of poly [(2-methoxy,5-n-octadecyl)-p-phenylenevinylene] (OC1OC18-PPV)

A PPV derivative, poly(2-methoxy,5-(n-octadecyl)-p-phenylenevinylene) (OC1OC18-PPV), has been synthesized via the Gilch route and used to fabricate Langmuir and Langmuir-Blodgett (LB) films. True monomolecular films were formed at the air/water interface, which were successfully transferred onto different types of substrate. Using UV-visible absorption, FTIR, fluorescence and Raman scattering spectroscopies we observed that the polymer molecules were randomly distributed in the LB film, with no detectable anisotropy. This is in contrast to the anisotropic LB films of a previously reported PPV derivative, poly(2-methoxy-5-n-hexyloxy)-p-phenylenevinylene (OC1OC6-PPV), which is surprising because the longer chain of OC1OC18-PPV investigated here was expected to lead to more ordered films. As a consequence of the lack of order, LB films of OC1OC18-PPV exhibit lower photoconductivity and require higher operating voltage in a polymer light-emitting diode (PLED) in comparison with LB films of OC1OC6-PPV. This result confirms the importance of molecular organization in the LB film to obtain efficient PLEDs. (c) 2005 Elsevier Ltd. All rights reserved.

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine,hereafter named tetrapyridyl porphyrins with distinct central ions (2H(+), Zn(2+), Cu(2+), Ni(2+)). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl(3) solutions. The shift was larger for the non-substituted H(2)TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with on further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H(2)TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H(2)TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups. (C) 2008 Elsevier B.V. All rights reserved.

Temperature dependence of photoinduced birefringence in mixed Langmuir-Blodgett (LB) films of azobenzene-containing polymers

The temperature dependence of photoinduced birefringence was investigated for mixed Langmuir-Blodgett (LB) films from the homopolymer poly[4'-[[2-(methacryloyloxy)ethyl]ethyl-amino]-2-chloro-4-nitroazobenzene] (HPDR13) and cadmium stearate (Cdst) and from the copolymer 4-[N-ethyl-N-(2-hydroxyethyl)]amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) and CdSt. Birefringence was achieved by impinging a linearly polarized light on the LB films. The maximum birefringence achieved decreased with temperature as thermal relaxation of the chromophores was facilitated. The buildup curves for birefringence were fitted with biexponential functions representing distinctly different mechanisms with time constants. The first, fast process is thermally activated and may be represented by an Arrhenius process. The decay of birefringence after switching off the laser source was described by a Kohlraush-Williams-Watts (KWW) function, consistent with a distribution of relaxation times for the polymer system. Activation energies were obtained from Arrhenius plots of the rate constant of the exponential functions and KWW function, which showed that the buildup of birefringence was very similar for the two polymer systems. The decay, however, was slower for the LB film from MMA-DR13/CdSt. (C) 2002 Published by Elsevier B.V. Ltd.

Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

Polymer light emitting devices with Langmuir Blodgett (LB) films of a polyfluorene derivative

Polyfluorenes are promising materials for the emitting layer of polymer light emitting devices (PLEDs) with blue emission. In this work, we report on PLEDs fabricated with Langmuir-Blodgett (LB) films of a polyfluorene derivative, namely poly(9,9-di-hexylfluorenediyl vinylene-alt-1,4-phenylenevinylene) (PDHF-PV). Y-type LB films were transferred onto ITO substrates at a surface pressure of 35 mN m-1 and with dipping speed of 3 mm min -1. A thin aluminum layer was evaporated on top of the LB film, thus yielding a sandwich structure (ITO/PDHF-PV(LB)/Al). Current-voltage (I vs V) measurements indicate that the device displays a classical behavior of a rectifying diode. The threshold value is approximately 5 V, and the onset for visible light emission occurs at ca. 10 V. From the a.c. electrical responses we infer that the active layer has a typical behavior of PLEDs where the real component of ac conductivity obeys a power-law with the frequency. Cole-Cole plots (Im(Z) vs. Re(Z)) for the device exhibit a series of semicircles, the diameter of which decreases with increasing forward bias. This PLED structure is modeled by a parallel resistance and capacitance combination, representing the dominant mechanisms of charge transport and polarization in the organic layer, in series with a resistance representing the ITO contact. Overall, the results presented here demonstrate the feasibility of LEDs made with LB films of PDHF-PV.

十八胺及其相关物质Langmuir-Blodgett膜的制备和性质研究

Langmuir-Blodgett（LB）膜技术由于在电子学、非线性光学以及化学传感器等领域具有潜在的应用前景而引起了人们的研究兴趣，其中它的热稳定性对LB膜的应用领域和范围具有一定的影响。本论文在此领域的主要研究内容如下： 利用LB膜技术分别制备了十八胺及硬脂酸、氘代硬脂酸的多层LB膜，采用变温傅立叶变换红外光谱研究了三种LB膜的相变行为。实验发现：十八胺LB膜在55-75 oC温度区间内发生相变，其CH2对称和反对称伸缩振动频率向高能量区发生明显移动；硬脂酸LB膜在70-80 oC的温度区间内发生了明显的相转变，CH2对称和反对称伸缩振动的强度比在升温过程中也有显著改变；氘代硬脂酸LB膜的相行为发生在65-70 oC的温度区间内。 利用LB膜技术制备了十八铵硬脂酸盐(C18H37NH3+C17H35COO-, ODASA)与十八铵氘代硬脂酸盐(C18H37NH3+C17D35COO-, ODASA-d35) Langmuir-Blodgett (LB)膜，使用变温傅立叶变换红外透射光谱研究了它们的热行为。发现LB膜中十八铵硬脂酸盐分子的两个碳氢链高度有序，然而在十八铵氘代硬脂酸盐LB分子中的来自于十八胺的碳氢链部分无序，即在常温下有一些扭曲构象存在于碳氢链中。而十八铵硬脂酸盐的热稳定性也与十八铵氘代硬脂酸盐的热稳定性有些不同。在十八铵硬脂酸盐LB膜中，碳氢链在85 oC到90 oC的温度区间内发生非常明显的有序-无序变化。而在十八铵氘代硬脂酸盐LB膜中，碳氢链和来自于硬脂酸的氘代的烃链各自呈现出不同的热行为，即：碳氢链在80-90 oC的温度区间发生有序-无序变化，尤其是在80-85 oC的温度范围内这个变化非常显著；而氘代的烃链则在70 oC到85 oC这个较长的温度区间发生缓慢的相变。 分别制备了十八铵十二酸盐 （C18H37NH3+C11H23COO-，ODALA）和十八铵二十四酸盐（C18H37NH3+C23H45COO-,ODATA）LB膜，并用变温傅立叶变换红外透射光谱法研究了十八铵十二酸盐和十八铵二十四酸盐LB膜的热行为，比较了十八铵十二酸盐、十八铵硬脂酸盐和十八铵二十四酸盐这三种双链化合物LB膜的热行为。温度相关的红外光谱显示，这三种物质LB膜的热稳定性取决于碳链的长度。其中，十八铵十二酸盐LB膜在50-65 oC的温度区间内发生相变。对应的，十八铵二十四酸盐LB膜在80-90 oC的温度范围内发生有序-无序变化。令人感兴趣的是，十八铵二十四酸盐LB膜的相变温度与十八铵硬脂酸盐LB膜的相变温度基本一样，都是80-90 oC，也即在十八铵二十四酸盐和十八铵硬脂酸盐两种LB膜中，即使二十四酸取代了硬脂酸对前者的热稳定性的影响非常小。以上结果说明，在双长链化合物中，有效链长度取决于双链中的较短的那个烃链，从而来决定膜的热稳定性。在十八铵二十四酸盐LB膜中，十八胺的全部碳链对膜的热稳定性有贡献，而二十四酸的碳链则只有部分（有效部分）烃链有贡献。 制备了十八胺单层和多层LB膜和粒径为几个纳米的金纳米粒子。由于十八胺在pH值小于10.3的溶液中氨基带正电荷，使其置于金纳米溶胶中，利用带正电荷的十八胺和附着负电荷的金纳米粒子之间的静电作用，使得金纳米颗粒成功地吸附组装到十八胺的有序分子膜中，形成有规律的纳米颗粒层。通过紫外-可见光谱、红外光谱以及扫描电镜观察到，金纳米颗粒通过这种方法能够很好的组装在有机分子膜上，而且由于十八胺LB膜的高度有序性使得金纳米颗粒的组装层有序。而且，不同层数的十八胺LB膜对金纳米粒子呈现出不同的吸附行为。 测量了含微量甲醇（体积分数为0.04%~0.24%）的系列乙醇水溶液的近红外光谱，利用近红外光谱分析建立了预测甲醇含量的定量分析模型。比较了用外部检验法（Test Set-Validation）和交叉检验法(Cross-Validaton)建立的数学模型以及研究了使用外部检验法时校正集和检验集样品数的改变对模型预测结果的影响。结果发现，当校正集样品数为15检验集样品数为6（总样品数为21）时，使用外部检验法建立的数学模型预测结果较好，外部检验与交叉检验的预测均方根误差（分别为RMSEE和RMSEP）都较小（分别为0.0105和0.0115）而且很接近。结果表明，近红外光谱方法简单，准确而且实用。

Study on mixed Langmuir-Blodgett film of tri-(2,4-di-t-amylphenoxy)-(8-quinolinolyl)copper phthalocyanine and water-soluble fullerenols

Mixed Langmuir-Blodgett films of tri-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine and water-soluble fullerenols are prepared. Their behavior at the air-water interface and the monolayer morphology are studied. (C) 1998 Elsevier Science Limited. All rights reserved.