Study of the interaction between cardiolipin bilayers and methylene blue in polymer-based Layer-by-Layer and Langmuir films applied as membrane mimetic systems

An increase of the reports involving mimetic systems has been observed. Briefly, these systems use biological phospholipids to exploit specific interactions between membrane-models and drugs. Here, the Layer-by-Layer (LbL) and Langmuir techniques were used to investigate the interaction between cardiolipin (CLP-negative phospholipid) and a cationic-like drug methylene blue (MB). Supported by a cationic polyelectrolyte (PAH), LbL films containing PAH/(CLP + MB) and PAH/(CLP + MB + AgNP) were grown up to 14 bilayers. The optical microscopy analysis revealed a decrease of the CLP vesicle sizes in the presence of MB as a possible consequence of the MB action onto the mechanical properties of the CLP membrane. From FTIR spectra, changes mainly related to peak position and band intensity and shape were observed in the spectra from PAH/CLP when in the presence of MB. The latter supports that the interactions between the phosphate and amine charged groups from CLP and PAH, respectively, established during the LbL film fabrication, besides the CLP hydrocarbon environment, are influenced by the presence of MB. Using the micro-Raman technique, a chemical mapping was build based on MB spectrum by resonance Raman scattering (RRS) and surface-enhanced resonance Raman scattering (SERRS). The later phenomenon was activated by Ag nanoparticles (AgNPs) trapped within the LbL film allowing collecting spectra for a single bilayer of PAH/(CLP + MB + AgNP). A rough estimation showed a SERRS amplification of 10(3) in comparison to RRS spectra. As a complementary approach, Langmuir films of CLP in the presence of co-spread MB were investigated through surface pressure vs mean molecular area (pi-A) isotherms. The results showed that for concentrations of MB below 100 mol%, the drug is expelled to water subphase for high values of surface pressure (condensed phase). For concentration at 100% and higher, the MB keeps bound to CLP floating monolayer. (C) 2010 Elsevier B.V. All rights reserved.

Spray layer-by-layer films based on phospholipid vesicles aiming sensing application via e-tongue system

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

Evaluation of the Smear Layer and Hybrid Layer in Noncarious and Carious Dentin Prepared by Air Abrasion System and Diamond Tips

Purpose: To analyze the smear layer and the hybrid layer in noncarious and carious dentin prepared by different cutting instruments and restored with composite resin. Study design: Cavities were randomly prepared in 160 specimens (noncarious and artificial carious dentin) by high-speed diamond tips (KG Sorensen 1013), air abrasion system (Prepstart, Danville Engineering), ultrasonic tip (CVDentus 8.3231-1), and ultrasonic tip associated with ultrasonic cavitation by water for 10 s. Half of the cavities in each group were conditioned with 37% phosphoric acid for 15 s. The amount of smear layer and dentinal tubules present were analyzed using scanning electron microscopy and graded from 0 to 3. Cavities were prepared in another 20 noncarious specimens and 20 carious specimens and restored with adhesive composite resin system. The restorations were hemisected longitudinally and analyzed using scanning electron microscopy to evaluate the hybrid layer and resinous prolongation characteristics, using scores ranging from 1 to 6. Results: The data were statistically analyzed using Kruskal-Wallis and Dunn tests at 5% of significance level. There was evidence that the most efficient smear layer removal was the acid etching in the noncarious dentin and the water ultrasonic cavitation in the carious dentin. The hybrid layer formed on the noncarious and carious dentin prepared by the ultrasonic tip was more regular than in the specimens prepared by high-speed diamond tip, with many resinous prolongations. Conclusion: The ultrasonic tip seems to be a promising tool for carious dentin cavity preparation. Microsc. Res. Tech. 73:597-605, 2010. (C) 2009 Wiley-Liss, Inc.

The traceability of animal meals in layer diets as detected by stable carbon and nitrogen isotope analyses of eggs

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

Identification of Mycobacteria by Thin Layer Chromatographic Analysis of Mycolic Acids and Conventional Biochemical Method: Four Years of Experience

Mycolic acids analysis by thin-layer chromatography (TLC) has been employed by several laboratories worldwide as a method for fast identification of mycobacteria. This method was introduced in Brazil by our laboratory in 1992 as a routine identification technique. Up to the present, 861 strains isolated were identified by mycolic acids TLC and by standard biochemical tests; 61% out of these strains came as clinical samples, 4% isolated from frogs and 35% as environmental samples. Mycobacterium tuberculosis strains identified by classical methods were confirmed by their mycolic acids contents (I, III and IV). The method allowed earlier differentiation of M. avium complex - MAC (mycolic acids I, IV and VI) from M. simiae (acids I, II and IV), both with similar biochemical properties. The method also permitted to distinguish M. fortuitum (acids I and V) from M. chelonae (acids I and II) , and to detect mixed mycobacterial infections cases as M. tuberculosis with MAC and M. fortuitum with MAC. Concluding, four years experience shows that mycolic acids TLC is an easy, reliable, fast and inexpensive method, an important tool to put together conventional mycobacteria identification methods.

Layer-by-layer 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 (LBL) technique. The films were characterized by vibrational analyses which indicated that the interactions between the two components lead to different properties in the films when compared to sol-gel films. of the neat compounds. In particular, using surface enhanced Raman scattering we were able to probe LBL film properties that depend on which material comprises the topmost layer.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Catechol biosensing using a nanostructured layer-by-layer film containing Cl-catechol 1,2-dioxygenase

dThe detection of aromatic compounds from pesticides and industrial wastewater has become of great interest, since these compounds withstand chemical oxidation and biological degradation, accumulating in the environment. In this work, a highly sensitive biosensor for detecting catechol was obtained with the immobilization of Cl-catechol 1,2-dioxygenase (CCD) in nanostructured films. CCD layers were alternated with poly(amidoamine) generation 4 (PAMAM G4) dendrimer using the electrostatic layer-by-layer (LbL) technique. Circular dichroism (CD) measurements indicated that the immobilized CCD preserved the same conformation as in solution. The thickness of the very first CCD layers in the LbL films was estimated at ca. 3.6 nm, as revealed by surface plasmon resonance (SPR). PAMAM/CCD 10-bilayer films were employed in detecting diluted catechol solutions using either an optical or electrical approach. Due to the mild immobilization conditions employed, especially regarding the pH and ionic strength of the dipping solutions, CCD remained active in the films for periods longer than 3 weeks. The optical detection comprised absorption experiments in which the formation of cis-cis muconic acid, resulting from the reaction between CCD and catechol, was monitored by measuring the absorbance at 260 nm after film immersion in catechol solutions. The electrical detection was carried out using LbL films deposited onto gold-interdigitated electrodes immersed in aqueous solutions at different catechol concentrations. Using impedance spectroscopy in a broad frequency range (1Hz-1kHz), we could detect catechol in solutions at concentrations as low as 10(-10) M. (c) 2005 Elsevier B.V. All rights reserved.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Use of conventional electrochemical techniques to produce crystalline FeRh alloys induced by Ag seed layer

By combining galvanic displacement and electrodeposition techniques, an ordered Fe20Rh80 structure deposited onto brass was investigated by X-ray diffractometry, Mössbauer spectroscopy and magnetization measurements. Mössbauer and X-ray diffraction analyses suggest that the Fe-Rh alloy directly electrodeposited onto brass displays a nanocrystalline state while a similar alloy deposited onto Ag/brass shows a faced centered cubic-like structure, with dendrites-like features. These results directly indicate that the presence of Ag seed layer is responsible for the Fe-Rh alloy crystallization process. In addition, room temperature Mössbauer data indicate firstly paramagnetic states for two Fe-species. In the dominant Fe-species (major fraction of the Mössbauer spectra), Fe atoms are situated at a cubic environment and it can be attributed to the γ-Fe20Rh80 alloy based on their hyperfine parameters. In the second species, Fe atoms are placed in a non-local symmetry, which can be related to Fe atoms at the grain boundaries or/and Fe small clusters. These Fe-clusters are in superparamagnetic state at room temperature, but they may be ordered below 45 K, as suggested by magnetization data. © 2013 Elsevier B.V. All rights reserved.

Molecularly designed layer-by-layer (LbL) films to detect catechol using information visualization methods

The control of molecular architectures has been exploited in layer-by-layer (LbL) films deposited on Au interdigitated electrodes, thus forming an electronic tongue (e-tongue) system that reached an unprecedented high sensitivity (down to 10-12 M) in detecting catechol. Such high sensitivity was made possible upon using units containing the enzyme tyrosinase, which interacted specifically with catechol, and by processing impedance spectroscopy data with information visualization methods. These latter methods, including the parallel coordinates technique, were also useful for identifying the major contributors to the high distinguishing ability toward catechol. Among several film architectures tested, the most efficient had a tyrosinase layer deposited atop LbL films of alternating layers of dioctadecyldimethylammonium bromide (DODAB) and 1,2-dipalmitoyl-sn-3-glycero-fosfo-rac-(1-glycerol) (DPPG), viz., (DODAB/DPPG)5/DODAB/Tyr. The latter represents a more suitable medium for immobilizing tyrosinase when compared to conventional polyelectrolytes. Furthermore, the distinction was more effective at low frequencies where double-layer effects on the film/liquid sample dominate the electrical response. Because the optimization of film architectures based on information visualization is completely generic, the approach presented here may be extended to designing architectures for other types of applications in addition to sensing and biosensing. © 2013 American Chemical Society.

Estudo da arquitetura molecular de filmes layer-by-layer de ftalocianina tetrasulfonada de cobre

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Determination of mercury in river water by diffusive gradients in thin films using P81 membrane as binding layer

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

Monoamine oxidase B layer-by-layer film fabrication and characterization toward dopamine detection

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