Electrochemical sensing of ethylene employing a thin ionic-liquid layer.

We introduce an electrochemical ethylene sensor that employs a thin layer of ionic liquid as electrolyte. Ethylene is oxidized in a potential window starting ∼600 mV before the onset of the gold working electrode oxidation, which inhibits the ethylene oxidation at high applied potential. The current amplitude and sensor response time depend on the ionic-liquid film thickness, relative humidity, and applied potential, in agreement with a theoretical model based on diffusion. A detection limit of 760 ppb and a linear response up to 10 ppm were achieved. As illustrated by the detection of ethylene, ionic liquids could serve as an alternative electrolyte for many electrochemical gas sensors that heretofore relied on a strongly acidic electrolyte.

Local probe oxidation of self-assembled monolayers: templates for the assembly of functional nanostructures.

The local oxidation of self-assembled monolayers with a scanning probe is a promising method for the generation of structures with chemical functionalities on the nanometer scale. This technique, which takes advantage of the chemical stability and versatility of self-assembled monolayers and the ability to pattern these monolayers by scanning-probe-based oxidation methods, enables the hierarchical assembly of complex structures in a controlled manner. Surface modification can be followed by the assembly of a further functional monolayer and/or additional surface-modification reactions in the targeted, sequential construction of functional device features.

Tuning solution polymer properties by binary -solvent mixtures.

The solubility of polymers can be significantly altered by the use of solvent mixtures. The solvent composition also effects the self-assembly properties of amphiphilic copolymers. In addition, water-ethanol mixtures are known to exhibit abnormal physicochemical properties due to the presence of hydration shells around the ethanol molecules, while at the same time both solvents have very low toxicity. However, the solution properties of amphiphilic copolymers in water-ethanol mixtures have been scarcely studied. Here we show that the solution polymer properties of amphiphilic copoly(2-oxazoline)s can be significantly altered in binary water-ethanol mixtures resulting in increased solubility, tuneable lower critical solution temperatures as well as polymer-solvent combinations with both a LCST followed by an UCST and improved dispersion stability. Surprisingly, it was found that polymers insoluble in both ethanol and water could be dissolved in water-ethanol mixtures, opening the way to novel formulations for drug delivery or personal care applications. Our results represent a straightforward method for tuning solution polymer properties without the synthetic efforts that are generally required to change the copolymer composition and properties.

Morphological transition during the thermal deprotection of poly(isobornyl acrylate)-b-poly(1-ethoxyethyl acrylate).

A set of poly(isobornyl acrylate)--poly(1-ethoxyethyl acrylate) polymers has been prepared by atom transfer radical polymerization. The 1-ethoxyethyl protecting group can be removed by a mild thermal treatment yielding the poly(acrylic acid) segment. The thin film morphological behavior of selected block copolymers was studied for as well as deprotected block copolymers using atomic force microscopy (AFM). Low-temperature thermal treatment yielded strongly phase-separated cylindrical features whereas treatment at temperatures above the glass transition temperature of the individual polymer blocks resulted in the initial generation of a similar phase contrast followed by a decrease in phase contrast caused by selective surface enrichment of the more hydrophobic poly(isobornyl acrylate) segment.

Oligonucleotide-protamine-albumin nanoparticles: Protamine sulfate causes drastic size reduction.

Nanoparticles prepared by self-assembly from oligonucleotides (ONs), protamine free base, and human serum albumin ("ternary proticles") are spheres of diameters around 200 nm. Substitution of the protamine free base by protamine sulfate leads to proticles of only around 40 nm in diameter with otherwise unchanged properties. The availability of drug delivery systems of very similar composition but grossly different size may be advantageous when dealing with cells which show size-dependent particle uptake. These nanoparticles are promising candidates for ON delivery to cells because of the following reasons: (1) They are stable for several hours in solutions of up to physiological ionic strength; (2) they are efficiently taken up by cells; (3) after cellular uptake, they easily release the ONs even when these are present as phosphorothioates.

Oligonucleotide-protamine-albumin nanoparticles: preparation, physical properties, and intracellular distribution.

Oligodesoxynucleotides (ODNs) or the corresponding phosphorothioates (PTOs) spontaneously form spherical nanoparticles ("proticles") with protamine in aqueous solutions. The proticles can cross cellular membranes and release the ODNs within the cells. Thus, they represent a potential drug delivery system. The major disadvantages of this system are a lack of stability in salt solutions and its inability to also release PTOs. The present study shows, using PTOs and protamine free base, that these shortcomings can be eliminated by the addition of human serum albumin (HSA) as a third component to the starting mixture. The "ternary" proticles thus obtained contain maximally a few percent of the HSA that was originally present. Nevertheless, they differ from the previously studied "binary" proticles: (1) They are stable in salt solutions for at least several hours. (2) They show a high cellular uptake into murine fibroblasts, and they readily release the PTOs after uptake. The ternary proticles therefore represent a considerable improvement over binary proticles for use as drug delivery systems.

Nanolithography and nanochemistry: probe-related patterning techniques and chemical modification for nanometer-sized devices.

The size regime for devices produced by photolithographic techniques is limited. Therefore, other patterning techniques have been intensively studied to create smaller structures. Scanning-probe-based patterning techniques, such as dip-pen lithography, local force-induced patterning, and local-probe oxidation-based techniques are highly promising because of their relative ease and widespread availability. The latter of these is especially interesting because of the possibility of producing nanopatterns for a broad range of chemical and physical modification and functionalization processes; both the production of nanometer-sized electronic devices and the formation of devices involving (bio)molecular recognition and sensor applications is possible. This Review highlights the development of various scanning probe systems and the possibilities of local oxidation methods, as well as giving an overview of state-of-the-art nanometer-sized devices, and a view of future development.

Block copolymer libraries: modular versatility of the macromolecular Lego system.

The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

Local probe oxidation of self-assembled monolayers on hydrogen-terminated silicon.

Local probe oxidation experiments by conductive AFM have been performed on a hexadecyl monolayer and a N-hydroxysuccinimide (NHS)-ester-functionalized undecyl (NHS-UA) monolayer assembled on hydrogen-terminated (i.e., unoxidized) silicon. The oxidation conditions for the mild oxidation of the top terminal groups of monolayers and the deep oxidation of the underlying silicon into silicon oxide were investigated. The results show that the bias threshold for the AFM tip-induced oxidation of the top groups of monolayers on oxide-free silicon can be reduced by 2 V for the methyl-terminated hexadecyl monolayer and even by 3.5 V for the active NHS-ester-terminated undecyl monolayer, in comparison to a methyl-terminated octadecyl trichlorosilane (OTS) monolayer on oxidized silicon. Upon such local mild oxidation, the active NHS ester group of the NHS-UA monolayer is selectively cleaved off to generate carboxyl-containing monolayer nanopatterns, opening further possibilities for subsequent patterned multifunctionalization.

Self-assembly of double hydrophobic block copolymers in water-ethanol mixtures: from micelles to thermoresponsive micellar gels.

Micellization and micellar gel formation of poly(styrene)-block-poly(methyl methacrylate) [PS-b-PMMA] are demonstrated in a water-ethanol solvent mixture; full hydration of the PMMA causes a large radius of gyration resulting in micellar gel formation at only 1 wt% polymer concentration.

Water-soluble ionic liquids as novel stabilizers in suspension polymerization reactions: engineering polymer beads.

Aqueous solutions of ionic liquids have been used as novel and environmentally friendly reaction media to synthesize and "control" the size of different cross-linked polymer beads by suspension polymerization reactions. It was found that the investigated ionic liquids can act as novel stabilizing agents of the suspensions as a result of their surface-active properties. The results have demonstrated that the average size of polymer beads can be varied from the macro- to the nanoscale and their surface area can also be "adjusted" by this synthetic approach. Furthermore, the use of a combination of ionic liquids and water for the synthesis of polymers, the simple isolation of the products formed in this polymerization procedure, as well as the recycling of the continuous medium for further reactions open up possibilities for the development of "new and green" polymerization processes.

Optimizing photo-embossed gratings: a gradient library approach.

Methodologies for the rapid screening of coating systems were developed and applied to photopolymer lacquers for photoembossing applications. Continuous and discrete gradient libraries were prepared with a gradient in grating period along the short axis and along the long axis, a gradient in exposure energy, development temperature, film thickness, photoinitiator concentration, or monomer to polymer mass ratio. Discrete gradient libraries consisted of arrays of rectangular films made by pipetting a certain amount of sample onto a chemically patterned substrate consisting of hydrophilic patches surrounded by hydrophobic, fluorinated barriers. The shape and height of the photoembossed gratings were measured using an automated AFM. Optimum grating height was obtained for a 20-microm period at intermediate exposure energies, photoinitiator concentrations, or both. Height improves with development temperature (max 110 degrees C), monomer-to-polymer ratio (max 55 wt % monomer), and film thickness. Surface topography can also be optimized, depending on any specific application.