In situ spectroscopic identification of the six types of asbestos.

Exposure to asbestos fibres is related to a number of severe lung diseases, and therefore, rapid, accurate and reliable in situ or on-site asbestos detection in real-life samples is of considerable importance. This work presents a comprehensive investigation of all six types of asbestos by mid-infrared ATR-FTIR, NIR spectroscopy and Raman microspectroscopy. Our studies demonstrate that for practical applications, NIR spectroscopy is potentially the most powerful method for asbestos identification in materials utilised by the construction industry. By focusing on the narrow spectral region, 7300-7000 cm-1 (~1370-1430 nm, overtones of O‒H vibrations), which is highly specific to these materials, and optimising the sensitivity and resolution of the instrumentation, we have been able to discriminate and identify each of the six types of asbestos with the level of detection significantly better than 1 wt%. Furthermore, straightforward computational analysis has allowed for automated objective evaluation of the spectroscopic data.

High-energy electron beam lithography of octadecylphosphonic acid monolayers on aluminum.

Monolayers of octadecylphosphonic acid were self-assembled on silicon substrates sputter coated with aluminum. Patterning of the self-assembled monolayer was achieved by high-energy electron (50 kV) illumination using an electron beam lithography tool. The change in chemical composition of the exposed monolayer was investigated by time-of-flight secondary ion mass spectrometry over an area of 100 x 100 microm2. The electron dose required to fully expose the SAM was found to be about 6 mC/cm2. Gratings were exposed with line widths from 10 microm to 100 nm. The resulting patterns were imaged using friction force microscopy. It was found that the minimum line width is limited to ca. 100 nm by the patterning resolution. The pattern resolution achieved, ca. 40 nm, is equal to the grain size of the sputter-coated aluminum layer, and the possibility that the grain size limits the pattern resolution is discussed.

Surface analysis under ambient conditions using plasma-assisted desorption/ionization mass spectrometry.

A novel plasma-assisted desorption/ionization (PADI) method that can be coupled with atmospheric pressure sampling mass spectrometry to yield mass spectral information under ambient conditions of pressure and humidity from a range of surfaces without the requirement for sample preparation or additives is reported. PADI is carried out by generating a nonthermal plasma which interacts directly with the surface of the analyte. Desorption and ionization then occur at the surface, and ions are sampled by the mass spectrometer. The PADI technique is demonstrated and compared with desorption electrospray ionization (DESI) for the detection of active ingredients in a range of over-the-counter and prescription pharmaceutical formulations, including nonsterodial anti-inflammatory drugs (mefenamic acid, Ibugel, and ibuprofen), analgesics (paracetamol, Anadin Extra), and Beecham's "all in one" cold and flu remedy. PADI has also been successfully applied to the analysis of nicotine in tobacco and thiosulfates in garlic. PADI experiments have been performed using a prototype source interfaced with a Waters Platform LCZ single-quadrupole mass spectrometer with limited modifications and a Hiden Analytical HPR-60 molecular beam mass spectrometer (MBMS). The ability of PADI to rapidly detect active ingredients in pharmaceuticals without the need for prior sample preparation, solvents, or exposed high voltages demonstrates the potential of the technique for high-throughput screening in a pharmaceutical or forensic environment.

Fabrication of biomolecular nanostructures by scanning near-field photolithography of oligo(ethylene glycol)-terminated self-assembled monolayers.

The UV photo-oxidation of oligo(ethylene glycol) (OEG)-terminated self-assembled monolayers (SAMs) has been studied using static secondary ion mass spectrometry, X-ray photoelectron spectroscopy, contact angle measurement, and friction force microscopy. OEG-terminated SAMs are oxidized to yield sulfonates, but photodegradation of the OEG chain also occurs on a more rapid time scale, yielding degradation products that remain bound to the surface via gold-sulfur bonds. The oxidation of these degradation products is the rate-limiting step in the process. Photopatterning of OEG-terminated SAMs may be accomplished by using a mask and suitable light source or by using scanning near-field photolithography (SNP) in which the mask is replaced by a scanning near-field optical microscope coupled to a UV laser. Using SNP, it is possible to fabricate patterns in SAMs with a full width at half-maximum height (fwhm) as small as 9 nm, which is approximately 15 times smaller than the conventional diffraction limit. SNP-patterned OEG-terminated SAMs may be used to fabricate protein nanopatterns. By adsorbing carboxylic acid-terminated thiols into oxidized regions and converting these to active ester intermediates, it has been possible to fabricate lines of protein molecules with widths of only a few tens of nanometers.

Infrared microscopy of epithelial cancer cells in whole tissues and in tissue culture, using synchrotron radiation.

Oral epithelial tumour tissue, and cultured cervical epithelial carcinoma cells have been studied using synchrotron infrared microspectroscopy. Mid infrared absorption spectra collected at cellular spatial resolution from within oral tumours were found to be sufficiently distinct, when analysed by principal component analysis, to distinguish between three different cell types within the tumour. The resulting data were sufficiently robust to allow correct classification of spectra from cells within subsequent tissue samples. These results go some way to demonstrate the potential of infrared spectroscopy as a tool in the post-operative screening of oral cancer patients by the examination of exfoliated epithelial cells. To gain a better understanding of the inherent variability in the infrared spectra of such epithelial cells, we have studied A431 carcinoma cells under the stimulus of the growth-stimulating hormone EGF. We have detected key changes in the infrared spectrum that relate to the activation of the growth factor signalling mechanism.