Bis amide-aromatic-ureasd - highly effective hydro- and organogelator systems

A series of hydro- and organo-supergelators have been synthesised via coupling of simple bis aromaticureas via alkyl amide linkages. These bis amide-aromatic-ureas exhibited reduced critical gelator concentrations, improved gelator stability, mechanical and dye removal properties for potential use in water purification, in comparison to related bis aromatic-ureas. Systematic structure studies via variation of the bis amide-aromatic-urea linker length as well as functionalization of the terminal aromatic moieties have enabled control over the gel properties.

Bis amide-aromatic-ureasd highly effective hydro- and organogelator systems

A series of hydro- and organo-supergelators have been synthesised via coupling of simple bis aromaticureas via alkyl amide linkages. These bis amide-aromatic-ureas exhibited reduced critical gelator concentrations, improved gelator stability, mechanical and dye removal properties for potential use in water purification, in comparison to related bis aromatic-ureas. Systematic structure studies via variation of the bis amide-aromatic-urea linker length as well as functionalization of the terminal aromatic moieties have enabled control over the gel properties.

POZylation: a new approach to enhance nanoparticle diffusion through mucosal barriers

The increasing use of nanoparticles in the pharmaceutical industry is generating concomitant interest in developing nanomaterials that can rapidly penetrate into, and permeate through, biological membranes to facilitate drug delivery and improve the bioavailability of active pharmaceutical ingredients. Here, we demonstrate that the permeation of thiolated silica nanoparticles through porcine gastric mucosa can be significantly enhanced by their functionalization with either 5 kDa poly(2-ethyl-2-oxazoline) or poly(ethylene glycol). Nanoparticle diffusion was assessed using two independent techniques; Nanoparticle Tracking Analysis, and fluorescence microscopy. Our results show that poly(2-ethyl-2-oxazoline) and poly(ethylene glycol) have comparable abilities to enhance diffusion of silica nanoparticles in mucin dispersions and through the gastric mucosa. These findings provide a new strategy in the design of nanomedicines, by surface modification or nanoparticle core construction, for enhanced transmucosal drug delivery.

Termination of diamond surfaces with hydrogen, oxygen and fluorine using a small, simple plasma gun

We have formed and characterized polycrystalline diamond films with surfaces having hydrogen terminations, oxygen terminations, or fluorine terminations, using a small, simple and novel plasma gun to bombard the diamond surface, formed by plasma assisted CVD in a prior step, with ions of the wanted terminating species. The potential differences between surface regions with different terminations were measured by Kelvin Force Microscopy (KFM). The highest potential occurred for oxygen termination regions and the lowest for fluorine. The potential difference between regions with oxygen terminations and hydrogen terminations was about 80 mV, and between regions with hydrogen terminations and fluorine terminations about 150 mV. Regions with different terminations were identified and imaged using the secondary electron signal provided by scanning electron microscopy (SEM). since this signal presents contrast for surfaces with different electrical properties. The wettability of the surfaces with different terminations was evaluated, measuring contact angles. The sample with oxygen termination was the most hydrophilic, with a contact angle of 75 degrees. hydrogen-terminated regions with 83 degrees, and fluorine regions 93 degrees, the most hydrophobic sample. (C) 2010 Elsevier B.V. All rights reserved.

On the Stabilization of Gold Nanoparticles over Silica-Based Magnetic Supports Modified with Organosilanes

The immobilization of gold nanoparticles (Au NPs) on silica is made possible by the functionalization of the silica surfaces with organosilanes. Au NPs could only be stabilized and firmly attached to silica-support surfaces that were previously modified with amino groups. Au NPs could not be stabilized on bare silica surfaces and most of the NPs were then found in the solution. The metal-support interactions before and after the Au NP formation, observed by X-ray absorption fine structure spectroscopy (XAFS), indicate a stronger interaction of gold-(III) ions with amino-modified silica surfaces than with the silanol groups in bare silica. An amino-modified, silica-based, magnetic support was used to prepare an active Au NP catalyst for the chemoselective oxidation of alcohols, a reaction of great interest for the fine chemical industry.

Electronic transport properties of ascorbic acid and nicotinamide adsorbed on single-walled carbon nanotubes

Ab initio simulations of carbon nanotubes interacting with ascorbic acid and nicotinamide are reported. The electronic transport properties of these systems are studied using a combination of density functional theory and non-equilibrium Green`s functions methods. The adsorptions of both molecules are observed to depend strongly on their functionalization. The interaction through the appropriate functionalized species modifies the structural and electronic properties of the original system, resulting in a chemisorption regime. Changes in the electronic transport properties are also observed, with reductions on the total electronic transmission probabilities. Nevertheless, when the molecules interact through the pristine form, a physisorption interaction is observed with insignificant structural and electronic transport changes. (c) 2011 Elsevier B.V. All rights reserved.

Realistic calculations of carbon-based disordered systems

Carbon nanotubes rank amongst potential candidates for a new family of nanoscopic devices, in particular for sensing applications. At the same time that defects in carbon nanotubes act as binding sites for foreign species, our current level of control over the fabrication process does not allow one to specifically choose where these binding sites will actually be positioned. In this work we present a theoretical framework for accurately calculating the electronic and transport properties of long disordered carbon nanotubes containing a large number of binding sites randomly distributed along a sample. This method combines the accuracy and functionality of ab initio density functional theory to determine the electronic structure with a recursive Green`s functions method. We apply this methodology on the problem of nitrogen-rich carbon nanotubes, first considering different types of defects and then demonstrating how our simulations can help in the field of sensor design by allowing one to compute the transport properties of realistic nanotube devices containing a large number of randomly distributed binding sites.

Boron and nitrogen functionalized diamondoids: A first principles investigation

Chemically functionalized adamantane molecules have been investigated by first principles total energy calculations. Boron and nitrogen functionalized molecules were found to be very stable, consistent with available experimental data. Two hypothetical molecular crystals, involving functionalized adamantane, were investigated. These molecular crystals presented direct electronic bandgaps and large bulk moduli, which suggested a possible road for molecular self-assembly using functionalized diamondoids. (C) 2010 Elsevier B.V. All rights reserved.

Optical Properties and Charge-Transfer Excitations in Edge-Functionalized All-Graphene Nanojunctions

We investigate the optical properties of edge-fiinctionalized graphene nanosystems, focusing on the formation of junctions and charge-transfer excitons. We consider a class of graphene structures that combine the main electronic features of graphene with the wide tunability of large polycyclic aromatic hydrocarbons. By investigating prototypical ribbon-like systems, we show that, upon convenient choice of functional groups, low-energy excitations with remarkable charge-transfer character and large oscillator strength are obtained. These properties can be further modulated through an appropriate width variation, thus spanning a wide range in the low-energy region of the UV-vis spectra. Our results are relevant in view of designing all-graphene optoelectronic nanodevices, which take advantage of the versatility of molecular functionalization, together with the stability and the electronic properties of graphene nanostructures.

Low-Frequency Noise in Field-Effect Devices Functionalized With Dendrimer/Carbon-Nanotube Multilayers

Low-frequency noise in an electrolyte-insulator- semiconductor (EIS) structure functionalized with multilayers of polyamidoamine (PAMAM) dendrimer and single-walled carbon nanotubes (SWNT) is studied. The noise spectral density exhibits 1/f(gamma) dependence with the power factor of gamma approximate to 0.8 and gamma = 0.8-1.8 for the bare and functionalized EIS sensor, respectively. The gate-voltage noise spectral density is practically independent of the pH value of the solution and increases with increasing gate voltage or gate-leakage current. It has been revealed that functionalization of an EIS structure with a PAMAM/SWNTs multilayer leads to an essential reduction of the 1/f noise. To interpret the noise behavior in bare and functionalized EIS devices, a gate-current noise model for capacitive EIS structures based on an equivalent flatband-voltage fluctuation concept has been developed.

Structure-Activity Relationship for Quaternary Ammonium Compounds Hybridized with Poly(methyl methacrylate)

Hybrid films from poly (methylmethacrylate) (PMMA) and dioctadecyldimethylammonium bromide (DODAB), cetyltrimethylammonium bromide (CTAB), or tetrapropylammonium bromide (TPAB) were characterized by determination of wettability, ellipsometry, atomic force microscopy, active compounds diffusion to water, X-ray photoelectron spectroscopy (XPS) with determination of atomic composition on the films surface, and biocidal activity against Pseudomonas aeruginosa or Staphylococcus aureus. QAC mobility in the films increased from DODAB to CTAB to TPAB. Diffusion and optimal hydrophobic hydrophilic balance imparted the highest bioactivity to CTAB. DODAB sustained immobilization at the film surface killed bacteria upon contact. TPAB ability to diffuse was useless because of its unfavorable hydrophobic hydrophilic balance for bioactivity.

Structure effects of self-assembled Prussian blue confined in highly organized mesoporous TiO(2) on the electrocatalytic properties towards H(2)O(2) detection

Here we report the derivatization of mesoporous TiO(2) thin films for the preparation of H(2)O(2) amperometric sensors. The coordination of the bifunctional ligand 1,10 phenantroline, 5,6 dione on the surface Ti(IV) ions provides open coordination sites for Fe(II) cations which are the starting point for the growth of a layer of Prussian blue polymer. The porous structure of the mesoporous TiO(2) allows the growth, ion by ion of the coordination polymer. Up to four layer of Prussian blue can be deposit without losing the porous structure of the film, which results in an enhanced response of these materials as H(2)O(2) sensors. These porous confined PB modified electrodes are robust sensors that exhibit good reproducibility, environmental stability and high sensitivity towards H(2)O(2) detection. (C) 2010 Elsevier B.V. All rights reserved.

Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Micro/nanostructured carbon composite modified with a hybrid redox mediator and enzymes as a glucose biosensor

A carbon micro/nanostructured composite based on cup-stacked carbon nanotubes (CSCNTs) grown onto a carbon felt has been found to be an efficient matrix for enzyme immobilization and chemical signal transduction. The obtained CSCNT/felt was modified with a copper hexacyanoferrate/polypyrrole (CuHCNFe/Ppy) hybrid mediator, and the resulting composite electrode was applied to H(2)O(2) detection, achieving a sensitivity of 194 +/- 15 mu A mmol(-1) L. The results showed that the CSCNT/felt matrix significantly increased the sensitivity of CuHCNFe/Ppy-based sensors compared to those prepared on a felt unrecovered by CSCNTs. Our data revealed that the improved sensitivity of the as-prepared CuHCNFe/Ppy-CSCNT/felt composite electrode can be attributed to the electronic interactions taking place among the CuHCNFe nanocrystals, Ppy layer and CSCNTs. In addition, the presence of CSCNTs also seemed to favor the dispersion of CuHCNFe nanocrystals over the Ppy matrix, even though the CSCNTs were buried under the conducting polymer layer. The CSCNT/felt matrix also enabled the preparation of a glucose biosensor whose sensitivity could be tuned as a function of the number of glucose oxidase (GOx) layers deposited through a Layer-by-Layer technique with an sensitivity of 11 +/- 2 mu A mmol(-1) L achieved at 15 poly(diallyldimethylammoniumchloride)/GOx bilayers. (C) 2011 Elsevier Ltd. All rights reserved.

Immobilization of Catalysts of Biological Interest on Porous Oxidized Silicon Surfaces

The present paper deals with the immobilization of redox mediators and proteins onto protected porous silicon surfaces to obtain their direct electrochemical reactions and to retain their bioactivities. This paper shows that MP-11 and viologens are able to establish chemical bonds with 3-aminopropyltriethoxylsilane-modified porous silicon surface. The functionalization of the surfaces have been fully characterized by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) to examine the immobilization of these mediators onto the solid surface. Amperometric and open circuit potential measurements have shown the direct electron transfer between glucose oxidase and the electrode in the presence of the viologen mediator covalently linked to the 3-aminopropyltriethoxylsilane (APTES)-modified porous silicon surfaces.