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Biomedical subjects

Manuel Marquez

Publications and source records attributed to Manuel Marquez.

35 records · Page 2Linked to original sources
PubMed2005

Anion binding studies of fluorinated expanded calixpyrroles.

The anion binding properties of fluorinated calix[n]pyrroles (n = 4-6) in aprotic solvents (acetonitrile and DMSO) and modified reaction conditions allowing for the synthesis and isolation of the hitherto missing dodecafluorocalix[6]pyrrole from the condensation of 3,4-difluoro-1H-pyrrole and acetone are described. In acetonitrile solution containing 2% water, the association constants for the 1:1 binding interaction between octafluorocalix[4]pyrrole and chloride anion obtained with isothermal titration calorimetry (ITC) and (1)H NMR titration methods were found to match reasonably well. As compared to its nonfluorinated congener, octafluorocalix[4]pyrrole was found to display enhanced binding affinities for several representative anions in pure acetonitrile as judged from ITC analyses. Similar analyses of the fluorinated calix[n]pyrroles revealed an increase in the relative affinity for bromide over chloride with increasing macrocycle size, as manifest in a decrease in the binding ratio K(a(Cl))/K(a(Br)). Anion binding studies in the solid state, involving single-crystal X-ray diffraction analyses of the chloride and acetate anion complexes of octafluorocalix[4]pyrrole and decafluorocalix[5]pyrrole, respectively, confirmed the expected hydrogen bond interactions between the pyrrolic NH protons and the bound anions.

Journal Article↗
PubMed2005

Rapid fixation of methylene chloride by a macrocyclic amine.

A simple macrocyclic amine is alkylated by methylene chloride to give a quaternary ammonium chloride salt. When methylene chloride is the solvent, the reaction exhibits pseudo-first-order kinetics, and the reaction half-life at 25.0 degrees C is 2.0 min. The reaction half-life for a structurally related, acyclic amine is approximately 50 000 times longer. Detailed calculations favor a mechanism where the methylene chloride associates with the macrocycle to form an activated prereaction complex. The macrocyclic nitrogen subsequently attacks the methylene chloride with a classic SN2 trajectory, and although the carbon-chlorine bond breaks, the chloride leaving group does not separate from the newly formed cationic macrocycle, such that the product is a tightly associated ion-pair. X-ray crystal structures of the starting amine and the product salt, as well as kinetic data, support this mechanism.

Journal Article↗
PubMed2005

Self-assembled shells composed of colloidal particles: fabrication and characterization.

We construct shells with tunable morphology and mechanical response with colloidal particles that self-assemble at the interface of emulsion droplets. Particles self-assemble to minimize the total interfacial energy, spontaneously forming a particle layer that encapsulates the droplets. We stabilize these layers to form solid shells at the droplet interface by aggregating the particles, connecting the particles with adsorbed polymer, or fusing the particles. These techniques reproducibly yield shells with controllable properties such as elastic moduli and breaking forces. To enable diffusive exchange through the particle shells, we transfer them into solvents that are miscible with the encapsulant. We characterize the mechanical properties of the shells by measuring the response to deformation by calibrated microcantilevers.

Colloids↗
PubMed2005

Calix[n]bispyrrolylbenzenes: synthesis, characterization, and preliminary anion binding studies.

A series of novel calixpyrrole-like macrocycles, calix[n]bis(pyrrol-2-yl)benzene (calix[n]BPBs, n=2-4) 9 a-11 a, have been synthesized by means of the TFA-catalyzed condensation reaction of bis(pyrrol-2-yl)benzene 8 a with acetone. Calix[2]BPB 9 a represents an expanded version of calix[4]pyrrole in which two of the four meso bridges are replaced by benzene rings. By contrast, systems 10 a and 11 a, which bear great considerable to calixbipyrroles 2 and 3, represent higher homologues of the basic calix[n]BPB motif. Solution-phase anion binding studies, carried out by means of (1)H NMR spectroscopic titrations in [D2]dichloromethane and isothermal titration calorimetry (ITC) in 1,2-dichloroethane, reveal that 9 a binds typical small anions with substantially higher affinities than 1, even though the same number of hydrogen bonding donor groups are found in both compounds. The basic building block for 9 a, benzene dipyrrole 8 a, also displays a higher affinity for anions than the building block for 1, dimethyldipyrromethane 16. Structural studies, carried out by single-crystal X-ray diffraction analyses, are consistent with the solution-phase results and reveal that 9 a is able to stabilize complexes with chloride and nitrate in the solid state. Structures of the PF6- and NO3- complexes of 10 a were also solved as were those of the acetone adduct of 9 a and the ethyl acetate adduct of 11 a.

Anions↗
PubMed2005

Diffusion coefficients in swelling polypyrrole: ESCR and Cottrell models.

Reliable diffusion coefficients, D, for the diffusion of perchlorate anions into polypyrrole films during polymeric oxidation were obtained from chronoamperometric results. Two different models were used to calculate D: the Cottrell equation and the electrochemically stimulated conformational relaxation (ESCR) model. As expected, the initial Cottrell hypothesis was far from swelling/shrinking polymeric electrodes and the obtained D range was from 10(-10) to 10(-6) cm(2) s(-1). The ESCR model, based on the internal diffusion that takes place from regions where the steady state of oxidation has already been reached to regions where the oxidation is only just beginning, provided values of D ranging from 0.4 x 10(-9) to 2.2 x 10(-9) cm(2) s(-1), which is close to the values expected for a gel. When a constant amplitude is kept for the potential step, D increases with increasing initial anodic potentials, i.e., from increasingly swollen films. When it is stepped to the same oxidation potential, D decreases when starting from more cathodic potentials, i.e., from a more compact structure. These changes in D can be attributed to (i) swelling processes during oxidation, giving a gel-like structure; (ii) compacting processes at increasing cathodic potentials; (iii) the increasing thickness of the film during oxidation; and (iv) a decrease in film viscosity during the swelling process.

Journal Article↗
PubMed2005

Monodisperse structured multi-vesicle microencapsulation using flow-focusing and controlled disturbance.

A method to produce monodisperse structured microcapsules in the diameter range from 10-100 microm is here presented. Flow-focusing is a well known technique whereby a steady capillary micro-jet is generated by the action of a highly accelerated co-flowing stream forced through a small orifice. The micro-jet breaks up owing to capillary instability, giving rise to droplets with a narrow size distribution. In the present study, flow-focusing gives rise not to simple but to compound capillary jets. At break-up, under suitable control parameters, such jets give rise to microcapsules where an outer liquid (shell liquid) surrounds a core liquid integrated by one or more vesicles. Furthermore, under adequate stimulation combining a sinusoidal signal with intermittent pulses, the jet break-up can be controlled. Highly monodisperse microcapsules are produced; fundamental geometric parameters (main diameter, shell thickness or number of cores) are reliably controlled. Rather than using a gas flow to focus the concentric stream of two immiscible liquids, this study has investigated in some detail the evolution of a concentric stream of three immiscible liquids forced through a small orifice. The selection of the surface tension coefficients between the three phases ensures the robust production of a microcapsule structure involving a plurality of vesicles homogeneously distributed in the capsule bulk, the number of cores being a freely chosen parameter. Such composite microcapsules find a broad field of technological applications in the pharmaceutical, food or biotechnology industries.

Drug Compounding↗
PubMed2004

Physically bonded nanoparticle networks: a novel drug delivery system.

Monodispersed nanoparticles consisting of interpenetrating polymer networks (IPNs) of polyacrylic acid (PAAc) and poly(N-isopropylacrylamide) (PNIPAM) were prepared by a seed-and-feed method. The temperature-dependent viscosity measurement revealed that the IPN nanoparticle dispersions with polymer concentrations above 2.5 wt.% underwent an inverse thermoreversible gelation at about 33 degrees C. Dextran markers of various molecular weights as model macromolecular drugs were mixed with the IPN nanoparticle dispersion at room temperature. At body temperature, the dispersion became a gel. The drug release profiles were then measured using UV-Visible spectroscopy as a function of particle size and polymer concentration. The schematic structure of the nanoparticle network was proposed based on the experimental results. The drug delivery model presented here was significant because such a dispersion and a drug was mixed without chemical reaction at room temperature to form a drug delivery liquid. This liquid could be injected into a body to form in situ a gelled drug depot to release the drug slowly.

Drug Delivery Systems↗
PubMed2004

Self-assembled polymer membrane capsules inflated by osmotic pressure.

We fabricate and characterize capsules that are composite membranes, made of a polymer network stabilized by adsorption to colloids and inflated by osmotic pressure from internal free polyelectrolyte; here, poly-l-lysine forms the network and inflates the capsules. To assess these capsules' properties and structure, we deform capsules using microcantilevers and use finite element modeling to describe these deformations. Additional experimental tests confirm the model's validity. These capsules' resilient response to mechanical forces indicates that loading and shear should be good triggers for the release of contents via deformation. The osmotic pressure inflating these capsules has the potential to trigger release of contents via deflation in response to changes in the capsules' environment; we demonstrate addition of salt as a trigger for deflating capsules. Because these capsules have a variety of release triggers available and the technique used to fabricate them is very flexible and allows high encapsulation efficiency, these capsules have very high potential for application in many areas.

Capsules↗
PubMed2004

Synthesis and self-assembly of nearly monodisperse nanoparticles of a naturally occurring polymer.

Nearly monodisperse nanoparticles have been synthesized based on a naturally occurring polymer of hydropropylcellulose (HPC) using precipitation polymerization method. It is found that when the polydispersity index value of the HPC nanoparticles is less than 1.10, the HPC particles can self-assemble into an ordered structure, displaying bright colors. UV-visible spectroscopy reveals that the color shifts to a lower wavelength as the interparticle distance decreases following the Bragg diffraction equation. The HPC nanoparticle assembly in water has been further stabilized by covalently bonding neighboring particles to form a three-dimensional network. This network contains a large amount of water similar to a conventional bulk gel but displays colors as a result of its ordered structure.

Biocompatible Materials↗
PubMed2004

Rapid direct nanowriting of conductive polymer via electrochemical oxidative nanolithography.

Conductive polymer nanolines having widths as small as 45 nm were obtained on glass using a novel scanning probe lithographic (SPL) technique at writing speeds of >5 mum/s. Herein we demonstrate that our nanowriting is >1500 times faster than current SPL nanoscale writing of conductive polymers. The lack of a specific restriction on the choice of substrates and the ability to write within a polymer matrix to provide a continuous film that is either 2-D or 2.5-D provide tremendous potential for our SPL technique in nanotechnology and plastic electronics applications.

Journal Article↗
PubMed2004

Structural and chemical characterization of monofluoro-substituted oligo(phenylene-ethynylene) thiolate self-assembled monolayers on gold.

Monolayers of oligo(phenylene-ethynylene) (OPE) molecules have exhibited promise in molecular electronic test structures. This paper discusses films formed from a novel molecule within this class, 2-fluoro-4-phenylethynyl-1-[(4-acetylthio)phenylethynyl]benzene (F-OPE). The conditions of self-assembled monolayer (SAM) formation were systematically altered to fabricate reproducible high-quality molecular monolayers from the acetate-protected F-OPE molecule. Detailed characterization of the F-OPE monolayers was performed by using an array of surface probes, including reflection absorbance infrared spectroscopy (RAIRS), contact angle (CA) measurements, spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and atomic force microscopy (AFM). XPS and RAIRS established that the SAM formed without removal of the F substituent and without oxidation of the thiol. The monolayer thickness, determined from SE and AFM based nanolithography, was consistent with the formation of a densely packed monolayer. The valence electronic structure of the SAM was consistent with an aromatic structure shifted by the electron-withdrawing fluorine substituent and intermolecular coupling within an oriented array of molecules.

Journal Article↗
PubMed2003

Fluorinated calixpyrroles: anion-binding extractants that reduce the Hofmeister bias.

Beta-octafluoro-meso-octamethylcalix[4]pyrrole (1) and beta-decafluoro-meso-decamethylcalix[5]pyrrole (2) were found to extract caesium salts of smaller anions (bromide and chloride for 1 and nitrate for 2) as effectively as that of iodide into nitrobenzene (NB) thereby overcoming the Hofmeister bias normally observed for processes of this type.

Journal Article↗
PubMed2003

A simple theoretical model to study the voltage dependence of the electronic structure of phenyl ethylene oligomers.

Although very few measurements have appeared in the open literature and there seems to be a controversy about the existence of the NDR phenomenon in molecules, the prospects of building such systems have attracted significant attention. In the work reported in this paper we used a model based on DFT calculations of the electronic structure of the 2'-amino-4,4'-di(ethynylphenyl)-5'-nitro-1-benzenethiolate molecule (previously reported to exhibit NDR behavior) in a capacitor-like electric field that mimics the potential spatial profile of the junction. Our results suggest that in these systems, there seems to be a correlation between a substantial charge density rearrangement of the neutral bridge at a threshold voltage and the NDR behavior observed in previous experiments. Our results highlight the importance of inclusion of the field in the study of electrified interfaces. We applied this model to a fluorine-substituted conjugated diethynylphenyl molecule and found that these calculations predict similar behavior. Results based on extended system calculations, including electrode-molecule interactions, confirm the validity of the model based on the isolated molecule and suggest the use of these simple models to rationally design molecular devices with similar switching characteristics.

Algorithms↗
PubMed2002

Colloidosomes: selectively permeable capsules composed of colloidal particles.

We present an approach to fabricate solid capsules with precise control of size, permeability, mechanical strength, and compatibility. The capsules are fabricated by the self-assembly of colloidal particles onto the interface of emulsion droplets. After the particles are locked together to form elastic shells, the emulsion droplets are transferred to a fresh continuous-phase fluid that is the same as that inside the droplets. The resultant structures, which we call "colloidosomes," are hollow, elastic shells whose permeability and elasticity can be precisely controlled. The generality and robustness of these structures and their potential for cellular immunoisolation are demonstrated by the use of a variety of solvents, particles, and contents.

Adsorption↗
PubMed2002

Multi-temporal self-organizations in 1,3-O,O'-bis(dodecyl)calix[4]arene.

After heat erases the order in 1,3-O,O'-bis(dodecyl)calix[4]arene, it self-organizes the phenyl units into a rigid calix bowl first at T2 = 111 degrees C, followed by the formation of all-trans alkyl chains at T1 = 62 degrees C, which eventually yields a stable cone-shaped structure at room temperature.

Calixarenes↗