Strong enhancement of gold nanoparticle chemiresistor response to low-partitioning organic analytes induced by pre-exposure to high partitioning organics.

Exposing a thiol-functionalised gold nanoparticle film chemiresistor to methanol in aqueous solution results in only a small electric current response as the thiol ligand/water partition coefficient of methanol is small, leading to only minor swelling of the chemiresistor film. Nevertheless, the current response to methanol can be enhanced if the chemiresistor becomes pre-exposed to a molecule with a large ligand/water partition coefficient P (e.g. octane with Po = 104.3). The large response enhancement is achieved because methanol, when added to an aqueous solution of octane, lowers the large initial partition coefficient of octane. Octane exiting the thiol ligands then leads to strong film shrinkage resulting in a relative current change much greater than the one otherwise induced by methanol alone. This was theoretically modelled for octane and heptane (Ph = 103.6). A strong response enhancement to methanol (>20 times) was observed experimentally by exposure to 2 ppm octane compared to direct testing of methanol in aqueous solution. Besides octane and heptane, molecules with P > 107 (e.g. permethrin) can theoretically be used to provide enhancement factors of several orders of magnitude. For practical reasons, heptane and octane saturate more quickly, thus enabling more rapid detection of methanol than higher P organic molecules.

Dynamic response of gold nanoparticle chemiresistors to organic analytes in aqueous solution.

We investigate the response dynamics of 1-hexanethiol-functionalized gold nanoparticle chemiresistors exposed to the analyte octane in aqueous solution. The dynamic response is studied as a function of the analyte-water flow velocity, the thickness of the gold nanoparticle film and the analyte concentration. A theoretical model for analyte limited mass-transport is used to model the analyte diffusion into the film, the partitioning of the analyte into the 1-hexanethiol capping layers and the subsequent swelling of the film. The degree of swelling is then used to calculate the increase of the electron tunnel resistance between adjacent nanoparticles which determines the resistance change of the film. In particular, the effect of the nonlinear relationship between resistance and swelling on the dynamic response is investigated at high analyte concentration. Good agreement between experiment and the theoretical model is achieved.

Gold nanoparticle chemiresistor sensor array that differentiates between hydrocarbon fuels dissolved in artificial seawater.

Gold nanoparticle films (Au(NPF)) functionalized with a range of hydrophobic and hydrophilic thiols were assembled in chemiresistor sensor arrays that were used to differentiate between complex mixtures of analytes in the aqueous phase. A chemiresistor array sampled a simple system of linear alcohols (methanol, ethanol, propan-1-ol, and butan-1-ol) dissolved in water over a range of concentrations. Discriminant analysis confirmed that the response patterns of the array could be used to successfully distinguish between the different alcohol solutions at concentrations above 20 mM for all of the alcohols except methanol, which was distinguished at concentrations above 200 mM. Alcohol solutions more dilute than these concentrations had response patterns that were not consistently recognizable and failed cross validation testing. This defined the approximate limit of discrimination for the system, which was close to the limits of detection for the majority of the individual sensors. Another Au(NPF) chemiresistor array was exposed to, and successfully identified crude oil, diesel, and three varieties of gasoline dissolved in artificial seawater at a fixed concentration. This work is a demonstration that the pattern of responses from an array of differently functionalized Au(NPF) sensors can be used to distinguish analytes in the aqueous phase.

Complex surface analytical investigations on hydrogen absorption and desorption processes of a TiMn2-based alloy.

Metal hydrides are one of the most promising technologies in the field of hydrogen storage due to their high volumetric storage density. Important reaction steps take place at the very surface of the solid during hydrogen absorption. Since these reaction steps are drastically influenced by the properties and potential contamination of the solid, it is very important to understand the characteristics of the surface, and a variety of analytical methods are required to achieve this. In this work, a TiMn(2)-type metal hydride alloy is investigated by means of high-pressure activation measurements, X-ray photoelectron spectroscopy (XPS), secondary neutral mass spectrometry (SNMS) and thermal desorption mass spectrometry (TDMS). In particular, TDMS is an analytical tool that, in contrast to SIMS or SNMS, allows the hydrogen content in a metal to be quantified. Furthermore, it allows the activation energy for desorption to be determined from TDMS profiles; the method used to achieve this is presented here in detail. In the results section, it is shown that the oxide layer formed during manufacture and long-term storage prevents any hydrogen from being absorbed, and so an activation process is required. XPS measurements show the oxide states of the main alloy elements, and a layer 18 nm thick is determined via SNMS. Furthermore, defined oxide layers are produced and characterized in UHV using XPS. The influence of these thin oxide layers on the hydrogen sorption process is examined using TDMS. Finally, the activation energy of desorption is determined for the investigated alloy using the method presented here, and values of 46 kJ/mol for hydrogen sorbed in UHV and 103 kJ/mol for hydrogen originating from the manufacturing process are obtained.

Influence of surface contaminations on the hydrogen storage behaviour of metal hydride alloys.

Hydrogen storage in metal hydrides is a promising alternative to common storage methods. The surface of a metal hydride plays an important part in the absorption of hydrogen, since important partial reaction steps take place here. The development of surface contaminations and their influence on hydrogen absorption is examined by means of absorption experiments and surface analysis, using X-ray photoelectron spectroscopy (XPS), thermal desorption mass spectrometry (TDMS) and secondary neutral mass spectrometry (SNMS), in this work. All investigations were carried out on a modern AB(2) metal hydride alloy, namely Ti(0.96)Zr(0.04)Mn(1.43)V(0.45)Fe(0.08). Surface analysis (SNMS, XPS) shows that long-term air storage (several months) leads to oxide layers about 15 nm thick, with complete oxidation of all main alloy components. By means of in situ oxygen exposure at room temperature and XPS analysis, it can be shown that an oxygen dose of about 100 Langmuirs produces an oxide layer comparable to that after air storage. Manganese enrichment (segregation) is also clearly observed and is theoretically described here. This oxide layer hinders hydrogen absorption, so an activation procedure is necessary in order to use the full capacity of the metal hydride. This procedure consists of heating (T = 120 degrees C) in vacuum and hydrogen flushing at pressures like p = 18 bar. During the activation process the alloy is pulverized to particles of approximately 20 microm through lattice stretches. It is shown that this pulverization of the metal hydride (creating clean surface) during hydrogen flushing is essential for complete activation of the material. Re-activation of powder contaminated by small doses of air (p approximately 0.1 bar) does not lead to full absorption capacity. In ultrahigh vacuum, hydrogen is only taken up by the alloy after sputtering of the surface (which is done in order to remove oxide layers from it), thus creating adsorption sites for the hydrogen. This is shown by TDMS measurements with and without sputtering and oxygen exposure.

GTP-Ras disrupts the intramolecular complex of C1 and RA domains of Nore1.

The novel Ras effector mNore1, capable of inducing apoptosis, is a multidomain protein. It comprises a C1 domain homologous to PKC and an RA domain similar to the Ras effectors AF-6 and RalGDS. Here, we determine the affinity of these two domains to the active forms of Ras and Rap1 using isothermal calorimetric titration. The interaction of Ras/Rap1-GTP with the RA domain of mNore1 is weakened significantly by direct binding of the C1 domain to the RA domain. In order to analyze this observation in atomic detail, we solved the C1 solution structure by NMR. By determining chemical shifts and relaxation rates, we can show an intramolecular complex of C1-RA. GTP-Ras titration and binding to RA disrupts this complex and displaces the C1 domain. Once the C1 domain tumbles freely in solution, a lipid binding interface becomes accessible. Furthermore, we provide evidence of phosphatidylinositol 3-phosphate binding of the free C1 domain.

Gold nanoparticle chemiresistors operating in biological fluids.

Functionalised gold nanoparticle (Au(NP)) chemiresistors are investigated for direct sensing of small organic molecules in biological fluids. The principle reason that Au(NP) chemiresistors, and many other sensing devices, have limited operation in biological fluids is due to protein and lipid fouling deactivating the sensing mechanism. In order to extend the capability of such chemiresistor sensors to operate directly in biofluids, it is essential to minimise undesirable matrix effects due to protein and lipidic components. Ultrafiltration membranes were investigated as semi-permeable size-selective barriers to prevent large biomolecule interactions with Au(NP) chemiresistors operating in protein-loaded biofluids. All of the ultrafiltration membranes protected the Au(NP) chemiresistors from fouling by the globular biomolecules, with the 10 kDa molecular weight cut-off size being optimum for operation in biofluids. Titrations of toluene in different protein-loaded fluids indicated that small molecule detection was possible. A sensor array consisting of six different thiolate-functionalised Au(NP) chemiresistors protected with a size-selective ultrafiltration membrane successfully identified, and discriminated the spoilage of pasteurised bovine milk. This proof-of-principle study demonstrates the on-chip protein separation and small metabolite detection capability, illustrating the potential for this technology in the field of microbial metabolomics. Overall, these results demonstrate that a sensor array can be protected from protein fouling with the use of a membrane, significantly increasing the possible application areas of Au(NP) chemiresistors ranging from the food industry to health services.