M. Mercedes Velázquez

Complexation of the Non-steroidal Anti-inflammatory Drug Nabumetone with Modified and Unmodified Cyclodextrins

The inclusion of the anti-inflammatory drug, Nabumetone, in α-, β- and hydroxypropyl-β-cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. 1H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring.

Graphene oxide thin films: influence of chemical structure and deposition methodology.

We synthesized graphene oxide sheets of different functionalization by oxidation of two different starting materials, graphite and GANF nanofibers, followed by purification based on alkaline washing. The chemical structure of graphene oxide materials was determined by X-ray photoelectron spectroscopy (XPS), and the nanoplatelets were characterized by ζ potential and dynamic light scattering (DLS) measurements. The XPS results indicated that the chemical structure depends on the starting material. Two different deposition methodologies, Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS), were employed to build the graphene oxide thin films. The film morphology was analyzed by scanning electron microscopy (SEM). The SEM images allow us to conclude that the LB methodology provides the highest coverage. This coverage is almost independent of the chemical composition of sheets. Conversely, the coverage obtained by the LS methodology increases with the percentage of C-O groups attached to sheets. Surface-pressure isotherms of these materials were interpreted according to the Volmer model.

Functionalization of Reduced Graphite Oxide Sheets with a Zwitterionic Surfactant

Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDPS) are obtained by using the Langmuir-Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X-ray photoelectron spectroscopy, atomic force microscopy (AFM), field-emission scanning electron microscopy (SEM), micro-Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation-based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO.

Hydrogen bonding in a non-steroidal anti-inflammatory drug—Naproxen

Photophysical properties of a non-steroidal anti-inflammatory drug, Naproxen (6-methoxy alpha-methyl-2-naphthalene acetic acid sodium salt), were investigated in solvents of different polarity, hydrogen donor ability and also in cyclodextrins. The results indicate that in all cases the emitting state is the 1L(b) singlet. In alcoholic solvents, an intermolecular hydrogen bond is responsible for the observed photophysical behaviour of the probe whereas in non-protic solvents (polar and weakly polar) an intramolecular hydrogen bond type is postulated to rationalize the data found. In water, the non-radiative rate constant has a value similar to those found in aqueous solutions of alpha- and beta-cyclodextrins where the probe form complexes. The behaviour in water is explained by a water-structure enforced hydrophobic effect. The spectroscopic results are interpreted on the basis of a multiple-parameter model that considers specific solute-solvent interactions. These were also observed in the ground state and detected by Fourier transform infrared spectroscopy. Molecular mechanics (MM) and molecular orbital (AM1) calculations also support the existence of two conformations (rotamers) in Naproxen with non-equivalent intramolecular hydrogen bond-like formation.

Langmuir and Langmuir−Blodgett Films of a Maleic Anhydride Derivative: Effect of Subphase Divalent Cations

We report the study of the equilibrium and dynamic properties of Langmuir monolayers of poly(styrene-co-maleic anhydride) partial 2-buthoxyethyl ester cumene terminated polymer and the effect of the Mg(NO(3))(2) addition in the water subphase on the film properties. Results show that the polymer monolayer becomes more expanded when the electrolyte concentration in the subphase increases. Dense polymer films aggregate at the interface. The aggregates are transferred onto silicon wafers using the Langmuir-Blodgett methodology and the morphology is observed by AFM. The structure of aggregates depends on the subphase composition of the Langmuir film transferred onto the silicon wafer.

Nanoparticle self-assembly assisted by polymers: the role of shear stress in the nanoparticle arrangement of Langmuir and Langmuir-Blodgett films.

We propose to use the self-assembly ability of a block copolymer combined with compression-expansion cycles to obtain CdSe quantum dots (QDs) structures of different morphology. The methodology proposed consists in transferring onto mica mixed Langmuir monolayers of QDs and the polymer poly(styrene-co-maleic anhydride) partial 2-butoxyethyl ester cumene terminated, PS-MA-BEE, previously sheared by 50 compression-expansion cycles. Results indicate that the shear stress takes out nanoparticles at the air-water interface from metastable states and promotes a new equilibrium state of the Langmuir monolayer. This new state was transferred onto mica by the Langmuir-Blodgett (LB) methodology, and the morphology of the LB films was analyzed by atomic force microscopy and transmission electron microscopy measurements. Our results show that when the amplitude strain increases, the QDs domain size decreases and the QDs LB film arrangement becomes more ordered. The dynamics of the monolayer relaxation after cycling involves at least three time scales which are related to the damping of surface fluctuation, raft rearrangement, and component movements inside each raft. Brewster angle microscopy allowed visualizing in situ the raft rearrangement at the air-water interface.

The Role of Oxidative Debris on Graphene Oxide Films

We study the effect of oxidative impurities on the properties of graphene oxide and on the graphene oxide Langmuir-Blodgett films (LB). The starting material was grupo Antolín nanofibers (GANF) and the oxidation process was a modified Hummers method to obtain highly oxidized graphene oxide. The purification procedure reported in this work eliminated oxidative impurities decreasing the thickness of the nanoplatelets. The purified material thus obtained presents an oxidation degree similar to that achieved by chemical reduction of the graphite oxide. The purified and non-purified graphene oxides were deposited onto silicon by means of a Langmuir-Blodgett (LB) methodology. The morphology of the LB films was analyzed by field emission scanning microscopy (FE-SEM) and micro-Raman spectroscopy. Our results show that the LB films built by transferring Langmuir monolayers at the liquid-expanded state of the purified material are constituted by close-packed and non-overlapped nanoplatelets. The isotherms of the Langmuir monolayer precursor of the LB films were interpreted according to the Volmers model.

Fluorescence quenching of pyrene by N-hexadecyl pyridinium chloride in mixed anionic micelles

A study of the fluorescence quenching of pyrene by N-hexadecyl pyridinium chloride in mixed micelles of sodium decyl and dodecyl sulphate, using a transient-state time-resolved fluorescence technique, enabled the determination of aggregation numbers and micellar volumes. The former vary between 49 to 65 and the latter between 16.6 and 20 dm3 mol–1 as the mole fraction of sodium dodecyl sulphate ranges from 0 to 1. A bimolecular rate constant to account for the electron transfer interaction was determined as 1.7 × 109 dm3 mol–1 s–1, regardless of the micellar size.

Effect of the Addition of Polyelectrolytes on Monolayers of Carboxybetaines

We have studied the effect of the addition of sodium poly(styrene sulfonate) polymers on the properties of monolayers formed by the adsorption of two carboxybetaines with different number of separation methylenes between their charged groups. Fluorescence and surface tension measurements indicate that above the critical aggregation concentration a surfactant-polymer complex of electrostatic origin is formed in bulk. The complexes have a negative charge that is repelled by the negative charge of the surfactant adsorbed at the interface; consequently, the monolayer seems to be exclusively formed by surfactant carboxybetaines. The high-frequency surface viscoelasticity of the monolayers was studied by surface dynamic light-scattering measurements. The behavior of the dilational elasticity and viscosity is explained by relaxation involving molecular reorientation within the adsorbed layer.

Modulating the Optoelectronic Properties of Silver Nanowires Films: Effect of Capping Agent and Deposition Technique

Silver nanowires 90 nm in diameter and 9 µm in length have been synthesized using different capping agents: polyvinyl pyrrolidone (PVP) and alkyl thiol of different chain lengths. The nanowire structure is not influenced by the displacement of PVP by alkyl thiols, although alkyl thiols modify the lateral aggregation of nanowires. We examined the effect of the capping agent and the deposition method on the optical and electrical properties of films prepared by Spray and the Langmuir-Schaefer methodologies. Our results revealed that nanowires capped with PVP and C8-thiol present the best optoelectronic properties. By using different deposition techniques and by modifying the nanowire surface density, we can modulate the optoelectronic properties of films. This strategy allows obtaining films with the optoelectronic properties required to manufacture touch screens and electromagnetic shielding.