Interaction of horseradish peroxidase with Langmuir monolayers of phospholipids

The method employed to incorporate guest molecules onto phospholipid Langmuir monolayers plays an important role in the interaction between the monolayer and the guest molecules. In this paper, we show that for the interaction between horseradish peroxidase (HRP) and a monolayer of dipalmitoylphosphatidylglycerol (DPPG) does depend on the method of HRP incorporation. The surface pressure isotherms of the mixed DPPG/HRP monolayers, for instance, were less expanded when the two materials were co-spread than in the case where HRP was injected into the subphase. Therefore, the method for incorporation affected not only the penetration of HRP but also the changes in molecular packing caused to the DPPG monolayer. With experiments with the monolayer on a pendant drop, we observed that the incorporation of HRP affects the dynamic elasticity of the DPPG monolayer, on a way that varies with the surface pressure. At low pressures, HRP causes the monolayer to be more rigid, while the converse is true for surface pressures above 8 mN/m. Taken all the results together, we conclude that HRP is more efficiently incorporated if injected into the subphase on which a DPPG monolayer had been spread and that the interaction between HRP and DPPG is maintained even at high surface pressures. This is promising for the possible transfer of mixed films onto solid substrates and for applications in biosensors and drug delivery systems. (c) 2008 Elsevier B.V. All rights reserved.

Enzyme Activity of Catalase Immobilized in Langmuir-Blodgett Films of Phospholipids

A major challenge for producing low cost biosensors based on nanostructured films with control of molecular architectures is to preserve the catalytic activity of the immobilized biomolecules. In this study, we show that catalase (HRP) keeps its activity if immobilized in Langmuir-Blodgett (LB) films of dipalmitoyl phosphatidylglycerol (DPPG). The incorporation of catalase into a DPPG monolayer at the at interface was demonstrated with surface pressure and surface potential isotherms, in addition to polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). According to the PM-IRRAS data. catalase was not denatured upon adsorption on a preformed DPPG monolayer and could be transferred onto a solid substrate. The catalytic activity of catalase in a mixed LB film with DPPG was ca. 13% higher than in solution. The control of molecular architecture and choice of a suitable phospholipid matrix allows catalase-containing LB films to be used in sensing hydrogen peroxide.

Mixing alternating copolymers containing fluorenyl groups with phospholipids to obtain Langmuir and Langmuir-Blodgett films

The control of molecular architectures may be essential to optimize materials properties for producing luminescent devices from polymers, especially in the blue region of the spectrum. In this Article, we report on the fabrication of Langmuir-Blodgett (LB) films of polyfluorene copolymers mixed with the phospholipid dimyristoyl phosphatidic acid (DMPA). The copolymers poly(9.9-dioetylfluorene)-co-phenylene (copolymer I) and poly(9,9-dioctylfluorene)-co-quaterphenylene) (copolymer 2) were synthesized via Suzuki reaction. Copolymer I could not form a monolayer on its own, but it yielded stable films when mixed with DMPA. In contrast, Langmuir monolayers could be formed from either the neat copolymer 2 or when mixed with DMPA. The surface pressure and surface potential measurements, in addition to Brewster angle microscopy, indicated that DMPA provided a suitable matrix for copolymer I to form a stable Langmuir film, amenable to transfer as LB films, while enhancing the ability of copolymer 2 to form LB films with enhanced emission, as indicated by fluorescence spectroscopy. Because a high emission was obtained with the mixed LB films and since the molecular-level interactions between the film components can be tuned by changing the experimental conditions to allow For further optimization, one may envisage applications of these films in optical devices such as organic light-emitting diodes (OLEDs).

Restoring the azimuthal symmetry of lateral distributions of charged particles in the range of the KASCADE-Grande experiment

The reconstruction of Extensive Air Showers (EAS) observed by particle detectors at the ground is based on the characteristics of observables like the lateral particle density and the arrival times. The lateral densities, inferred for different EAS components from detector data, are usually parameterised by applying various lateral distribution functions (LDFs). The LDFs are used in turn for evaluating quantities like the total number of particles or the density at particular radial distances. Typical expressions for LDFs anticipate azimuthal symmetry of the density around the shower axis. The deviations of the lateral particle density from this assumption arising from various reasons are smoothed out in the case of compact arrays like KASCADE, but not in the case of arrays like Grande, which only sample a smaller part of the azimuthal variation. KASCADE-Grande, an extension of the former KASCADE experiment, is a multi-component Extensive Air Shower (EAS) experiment located at the Karlsruhe Institute of Technology (Campus North), Germany. The lateral distributions of charged particles are deduced from the basic information provided by the Grande scintillators - the energy deposits - first in the observation plane, then in the intrinsic shower plane. In all steps azimuthal dependences should be taken into account. As the energy deposit in the scintillators is dependent on the angles of incidence of the particles, azimuthal dependences are already involved in the first step: the conversion from the energy deposits to the charged particle density. This is done by using the Lateral Energy Correction Function (LECF) that evaluates the mean energy deposited by a charged particle taking into account the contribution of other particles (e.g. photons) to the energy deposit. By using a very fast procedure for the evaluation of the energy deposited by various particles we prepared realistic LECFs depending on the angle of incidence of the shower and on the radial and azimuthal coordinates of the location of the detector. Mapping the lateral density from the observation plane onto the intrinsic shower plane does not remove the azimuthal dependences arising from geometric and attenuation effects, in particular for inclined showers. Realistic procedures for applying correction factors are developed. Specific examples of the bias due to neglecting the azimuthal asymmetries in the conversion from the energy deposit in the Grande detectors to the lateral density of charged particles in the intrinsic shower plane are given. (C) 2011 Elsevier B.V. All rights reserved.

Economic Evaluation of a Solar Charged Thermal Energy Store for Space Heating

A thermal energy store corrects the misalignment of heating demand in the winter relative to solar thermal energy gathered in the summer. This thesis reviews the viability of a solar charged hot water tank thermal energy store for a school at latitude 56.25N, longitude -120.85W

Signatures of doubly charged Higgs in the SU(3)(L) circle times U(1)(N) model at the CERN LHC

The scalar sector of the simplest version of the 3-3-1 electroweak model is constructed with three Higgs triplets only. We show that a relation involving two of the constants of the model, two vacuum expectation values of the neutral scalars, and the mass of the doubly charged Higgs boson leads to important information concerning the signals of this scalar particle.

Searching for doubly charged Higgs bosons at the LHC in a 3-3-1 model

Using a peculiar version of the SU(3)(L) circle times U(1)(N) electroweak model, we investigate the production of doubly charged Higgs boson at the Large Hadron Collider. Our results include branching ratio calculations for the doubly charged Higgs and for one of the neutral scalar bosons of the model. (c) 2006 Elsevier B.V. All rights reserved.

Doubly charged Higgs through photon-photon collisions in 3-3-1 models

We study the production and signatures of doubly charged Higgs bosons (DCHBs) in the process gamma gamma <-> H(--)H(++) at the e(-)e(+) International Linear Collider and CERN Linear Collider, where the intermediate photons are given by the Weizsacker-Willians and laser backscattering distributions.

Probing doubly charged Higgs bosons in e(+)e(-) colliders at the ILC and the CLIC in a 3-3-1 model

The SU(3)(L) circle times U(1)(N) electroweak model predicts new Higgs bosons beyond the one of the standard model. In this work we investigate the signature and production of doubly charged Higgs bosons in the e(+)e(-) International Linear Collider and in the CERN Linear Collider. We compute the branching ratios for the doubly charged gauge bosons of the model.

Layer-by-Layer Technique as a New Approach to Produce Nanostructured Films Containing Phospholipids as Transducers in Sensing Applications

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

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.

Combining SERRS and electrochemistry to characterize sensors based on biomembrane mimetic models formed by phospholipids

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

Effect of vesicles of dimethyldioctadecylammonium chloride and phospholipids on the rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate

Sonicated mixtures of dimethyldioctadecylammonium chloride (DODAC), egg phosphatidylcholine (PC), dimyristoyl phosphatidylcholine (DMPC), and dipalmitoyl phosphatidylcholine (DPPC) were used to analyze vesicle effects on the rate of decarboxylation of 6-nitrobenzisoxazol-3-carboxylic acid (Nboc). Electron microscopic images of the vesicles were obtained with trehalose, a know cryoprotector. Phase diagrams and phase transitions temperatures of the vesicle bilayers were determined. Nboc decarboxylation rates increased in the presence of vesicles prepared with both phospholipids and DODAC/phospholipid mixtures. Quantitative analysis of vesicular effects was done using pseudophase models. Phospholipids catalyzed up to 140-fold while the maximum catalysis by DODAC/lipid vesicles reached 800-fold. Acceleration depends on alkyl chain length, fatty acid insaturation of the lipids, and the DODAC/phospholipid molar ratio. Catalysis is not related to the liquid crystalline-gel state of the bilayer and may be related to the relative position of Nboc with respect to the interface.