Electroacoustic miniaturized DNA-biosensor

A micrometer-sized electroacoustic DNA-biosensor was developed. The device included a thin semi-crystalline polyethylene terephthalate (PET) dielectric layer with two Ag microband electrodes on one side and a DNA thiol-labeled monolayer adsorbed on a gold surface on the other. A resonance wave was observed at 29 MHz with a network analyzer, upon AC voltage application between the two Ag electrodes, corresponding to electromechanical coupling induced by molecular dipoles of the PET polymer chain in the dielectric layer. It was found that the device size and geometry were well adapted to detect DNA hybridization, by measuring the capacity of the resonance response evolution: hybridization induced polarization of the dielectric material that affected the electromechanical coupling established in the dielectric layer. The 0.2 mm(2) sensor sensitive area allows detection in small volumes and still has higher detection levels for bioanalytical applications, the non-contact configuration adopted avoids electric faradic reactions that may damage biosensor sensitive layers, and finally, PET is a costless raw material, easy to process and well adapted for large scale production. The well-balanced technological and economic advantages of this kind of device make it a good candidate for biochip integration.     

Pickering emulsions with stimulable particles: from highly- to weakly-covered interfaces

We study oil-in-water emulsions stabilised by pH-sensitive colloidal silica or latex particles. Depending on the composition of the continuous phase, the same type of particles and the same emulsification process lead to emulsions characterised either by large drops densely covered by the particles, or to small droplets which are weakly covered. The two kinetically stable states can be tuned reversibly by using pH or salinity as compositional stimuli. We examine the emulsions' behaviour in these two limiting cases and we discuss the possible mechanisms allowing stabilisation, especially in the case of low surface coverage.     

Guest-host colloid crystals: experimental study and simulations

Disorder in colloid crystals was induced by doping them with a different number of large or small guest particles, which had a different deviation in size from the host colloids. The change in optical properties of the guest-host colloid crystals was assessed by using optical transmission spectroscopy while the variation in crystal structure was examined using scanning electron microscopy (SEM). The disruption in the crystalline lattices depended on the relative deviation in sizes of the guest and host particles and the concentration of the guest colloids. In parallel with experiments, the packing of spheres in guest-host crystals was modeled with a simulated annealing algorithm. A good correlation was found between the changes in crystal structure observed by SEM imaging and the simulated sphere packing. The experimental and simulated changes in the transmission spectra of guest-host colloid crystals were in good agreement.     

Molecule-molecule versus molecule-substrate interactions in the assembly of oligothiophenes at surfaces

In this paper we present a joint experimental and theoretical approach for the study of the assembly of end-substituted oligothiophenes at surfaces with different polarities (i.e., mica vs graphite). Scanning probe microscopy studies of (sub)monolayer deposits show various types of structures (one-dimensional fibrils, two-dimensional regular layers, and monolayers), depending on the nature of the end groups and the substrate. Using molecular modeling with an atomistic approach, we focus on the interplay between the molecule-molecule (and segment-segment) interactions and the molecule-substrate interactions and their influence on the observed morphologies and the stacking geometry. Such information is relevant for controlling the structural order in thin layers of thiophene oligomers for use in field-effect transistor applications, for example, by modifying the nature of dielectric material over which those compounds are deposited.     

Influence of chlorine substitution on the self-assembly of zinc phthalocyanine

The adsorption and ordering of zinc phthalocyanine (ZnPc) and octachloro zinc phthalocyanine (ZnPcCl(8)) on an Ag(111) surface is studied in situ by scanning tunneling microscopy under ultrahigh vacuum. Two-dimensional self-assembled supramolecular domains are observed for these two molecules. We show how substituting chlorine atoms for half of the peripheral hydrogen atoms on ZnPc influences the self-assembly mechanisms. While intermolecular interactions are dominated by van der Waals forces in ZnPc molecular networks, ZnPcCl(8) molecular packing undergoes a sequential phase evolution driven by the creation of C-Cl...H-C hydrogen bonds between adjacent molecules. At the end of this evolution, the final molecular assembly involves all possible hydrogen bonds. Our study also reveals the influence of molecule-substrate interactions through the presence of fault lines generating a stripe structure in the molecular film.     

In vivo application of intestinal pH measurement using 2',7'-bis(carboxyethyl)-5,6-carboxyfluorescein (BCECF) fluorescence imaging

Measurement of gastrointestinal intramucosal pH (pHim) has been recognized as an important factor in the detection of hypoxia-induced dysfunctions. However, current pH measurement techniques are limited in terms of time and spatial resolutions. A major advance in accurate pH measurement was the development of the ratiometric fluorescent indicator dye, 2',7'-bis(carboxyethyl)-5,6-carboxyfluorescein (BCECF). This study aimed to set up and validate a fluorescence imaging technique to measure in vivo the intramucosal pH (pHim) of the intestine. The intestine was inserted into an optical chamber placed under a microscope. Animals were injected intravenously with the pH-sensitive fluorescent dye BCECF. Fluorescence was visualized by illuminating the intestine alternately at 490 and 470 nm. The emitted fluorescence was directed to an intensified camera. The ratio of emitted fluorescence at excitation wavelengths of 490 and 470 nm was measured, corrected and converted to pHim by constructing a calibration curve. The pHim controls were performed with a pH microelectrode and were correlated with venous blood gas sampling. Results show that pHim is determined with an accuracy of +/- 0.07 pH units and a response time of 1 min. In conclusion pHim mapping of rat intestine can be obtained by fluorescence imaging using BCECF. This technology could be easily adapted for endoscopic pH measurements.     

Underpotential deposition of hydrogen on benzene-modified Pt(111) in aqueous H2SO4

The Pt(111) electrode is modified by an overlayer of C6H6 (ads) upon its cycling in the 0.05-0.80 V range in aq H2SO4 + 1 mM C6H6. The C6H6 (ads) overlayer significantly changes the underpotential-deposited H (H(UPD)) and anion adsorption, and cyclic-voltammetry (CV) profiles show a sharp cathodic peak and an asymmetric anodic one in the 0.05-0.80 V potential range. The C6H6 (ads) layer blocks the (bi)sulfate adsorption but facilitates the adsorption of one monolayer of H(UPD). Cycling of the benzene-modified Pt(111) in benzene-free aq 0.05 H2SO4 from 0.05 to 0.80 V results in a partial desorption of C6H6 (ads) and in a partial recovery of the CV profile characteristic of an unmodified Pt(111). The peak potential of the cathodic and anodic feature is independent of the scan rate, s (10 < or = s < or = 100 mV s(-1)), and the peak current density increases linearly with an increase of the scan rate. Temperature variation modifies the peak potential and current density but does not affect the charge density of the cathodic or anodic feature. Temperature-dependent studies allow us to determine the thermodynamic state function for the H(UPD) adsorption and desorption. Delta G degrees(ads)(H(UPD))assumes values from -4 to -12 kJ mol(-1), while has values from 9 to 14 kJ mol(-1). The values of delta Delta G degrees (delta Delta G degrees = delat Delta G degrees(ads) + delta Delta D degrees(des)) decrease almost linearly from 6 kJ mol(-1) at theta(H(UPD) --> 0 to 0 kJ mol(-1) at theta(H(UPD) --> 1. The nonzero values of delta Delta G degrees testify that the adsorbing and desorbing H(UPD) adatoms interact with an energetically different substrate. The lateral interactions changed from repulsive (omega = 29 kJ mol(-1) at theta(H(UPD) --> 0) to attractive (omega = -28 kJ mol(-1) at theta(H(UPD) --> 1) as the H(UPD) coverage increases. The values of delta S degrees(ads)(H(UPD)) increase from 19 to 56 J K(-1) mol(-1), while those of delta S degrees(des)(H(UPD)) decrease from 45 to -30 J K(-1) mol(-1) with an increase of H(UPD) coverage. The values of delta H degrees(des)(H(UPD)) and delta H degrees(des)(H(UPD)) vary from 0 to 27 kJ mol(-1). The Pt(111)-H(UPD) surface bond energy at the benzene-modified Pt(111) electrode falls in the 191-218 kJ mol(-1) range and is weaker than in the case of the unmodified Pt(111) electrode in the same electrolyte.     

Design of organic semiconductors: tuning the electronic properties of pi-conjugated oligothiophenes with the 3,4-ethylenedioxythiophene (EDOT) building block

Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined.     

Electrochemical evidences of morphological transformation in ordered mesoporous titanium oxide thin films

We provide the first electrochemical evidence of permeability changes in continuous mesoporous TiO2 thin film electrodes induced by nanocrystallisation.