Layer-by-Layer Assembly of Carbon Nanotubes Incorporated in Light-Addressable Potentiometric Sensors

The integration of carbon nanotubes in conjunction with a chemical or biological recognition element into a semiconductor field-effect device (FED) may lead to new (bio)chemical sensors. In this study, we present a new concept to develop field-effect-based sensors, using a light-addressable potentiometric sensor (LAPS) platform modified with layer-by-layer (LbL) films of single-walled carbon nanotubes (SWNTs) and polyamidoamine (PAMAM) dendrimers. Film growth was monitored for each layer adsorbed on the LAPS chip by Measuring current-voltage (IIV) curves. The morphology of the films was analyzed via atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM), revealing the formation of a highly interconnected nanostructure of SWNTs-network into the dendrimer layers. Constant current (CC) Measurements showed that the incorporation of the PAMAM/SWNT LbL film containing LIP to 6 bilayers onto the LAPS Structure has a high pH sensitivity of ca. 58 mV/pH. The biosensing ability of the devices was tested for penicillin G via adsorptive immobilization of the enzyme penicillinase atop the LgL film. LAPS architectures modified with the LbL film exhibited higher sensitivity, ca. 100 mV/decade, in comparison to ca. 79 mV/decade for all unmodified LAPS, which demonstrates the potential application of the CNT-LbL Structure in field-effect-based (bio)chemical sensors.

Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy

The molecular arrangement in organic thin films is crucial for their increasing technological applications. Here, we use vibrational spectroscopy by sum-frequency generation (SFG) to study the ordering of polyelectrolyte layers adsorbed on silica for all steps of layer-by-layer (LbL) self-assembly. In situ measurements during adsorption and rinsing showed that the adsorbed polymer has a disordered conformation and confirmed surface charge overcompensation upon polyelectrolyte adsorption by probing the interfacial electric field. In dry films, the polymer chains acquired a net orientational ordering, which was affected, however, by the adsorption of subsequent layers. Such a detailed characterization may allow the control of LbL film structure and functionality with unprecedented power.

Modeling Adsorption Processes of Poly-p-phenylenevinylene Precursor and Sodium Acid Dodecylbenzenesulfonate onto Layer-by-Layer Films Using a Langmuir-type Metastable Equilibrium Model

The adsorption kinetics curves of poly(xylylidene tetrahydrothiophenium chloride) (PTHT), a poly-p-phenylenevinylene (PPV) precursor, and the sodium salt of dodecylbenzene sulfonic acid (DBS), onto (PTHT/DBS)(n) layer-by-layer (LBL) films were characterized by means of UV-vis spectroscopy. The amount of PTHT/DBS and PTHT adsorbed on each layer was shown to be practically independent of adsorption time. A Langmuir-type metastable equilibrium model was used to adjust the adsorption isotherms data and to estimate adsorption/desorption coefficients ratios, k = k(ads)/k(des), values of 2 x 10(5) and 4 x 10(6) for PTHT and PTHT/DBS layers, respectively. The desorption coefficient has been estimated, using literature values for poly(o-methoxyaniline) desorption coefficient, as was found to be in the range of 10(-9) to 10(-6) s(-1), indicating that quasi equilibrium is rapidly attained.

Molecular Ordering in Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy: The Effects of Drying Procedures

Sum-Frequency Vibrational Spectroscopy (SFVS) has been used to investigate the effect of nitrogen-flow drying on the molecular ordering of Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) (PAH) alternated with poly(styrene sulfonate) (PSS). We find that films dried by spontaneous water evaporation are more ordered and homogeneous than films dried by nitrogen flow. The latter are quite inhomogeneous and may have regions with highly disordered polymer conformation. We propose that drying by spontaneous water evaporation reduces the effect of drag by the drying front, while during nitrogen-flow drying the fast evaporation of water ""freezes"" the disordered conformation of adsorbed polyelectrolyte molecules. These findings are important for many applications of LbL films, since device performance usually depends on film morphology and its molecular structure.

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 liposonnes 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.

Adsorption kinetics and charge inversion in layer-by-layer films from nickel tetrasulfonated phthalocyanine and poly(allylamine hydrochloride)

Layer-by-layer (LBL) films of nickel tetrasulfonated phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) have been prepared, whose surface charge has been evaluated using surface potential measurements. From adsorption kinetics results, we obtained the immersion time of similar to 40 s, which was used to assemble layers of NiTsPc. The effect of gold (Au) and aluminum (Al) electrodes on the charge behavior was examined. We found that the surface potential (i.e. surface charge) was inverted each time a layer of PAH was alternated with another of NiTsPc molecules for the two types of electrodes, which was attributed to charge overcompensation between positive charges of PAH molecules, and negative charges from NiTsPc molecules. (C) 2009 Elsevier B.V. All rights reserved.

Immobilization of liposomes in nanostructured layer-by-layer films containing dendrimers

Artificial vesicles or liposomes composed of lipid bilayers have been widely exploited as building blocks for artificial membranes, in attempts to mimic membrane interaction with drugs and proteins and to investigate drug delivery processes. In this study we report on the immobilization of liposomes of 1,2-dipalmitoyi-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) in layer-by-layer (LbL) films, alternated with poly (amidoamine) G4 (PAMAM) dendrimer layers. The average size of the liposomes in solution was 120 nm as determined by dynamic light scattering, with their spherical shape being inferred from scanning electron microscopy (SEM) in cast films. LbL films containing up to 20 PAMAM/DPPG bilayers were assembled onto glass and/or silicon wafer substrates. The growth of the multilayers was achieved by alternately immersing the substrates into the PAMAM and DPPG solutions for 5 and 10 min, respectively. The formation of PAMAM/DPPG liposome multilayers and its ability to interact with BSA were confirmed by Fourier transform infrared spectroscopy (FTIR). The structural features and film thickness were obtained using X-ray diffraction and surface plasmon resonance (SPR). (c) 2007 Elsevier B.V. All rights reserved.

Electrostatic layer-by-layer and electrophoretic depositions as methods for electrochromic nanoparticle immobilization

The present paper describes the immobilization of nanoparticles onto conducting substrates by using both electrostatic layer-by-layer and electrophoretic deposition (EPD) methods. These two techniques were compared in high-performance electrochromic electrodes based on mixed nickel hydroxide nanoparticles. In addition to easy handling, EPD seems to be the most suitable method for the immobilization of nanoparticles, leading to higher electrochromic efficiencies, lower response times and higher stability upon coloration and bleaching cycling. (C) 2008 Elsevier Ltd. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.