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Barkcloths, non-woven textiles originating from the Pacific Islands, form part of many museum collections and date back to the 18th and 19th centuries. The ability to determine different plant species which have been used for producing barkcloth is required by art historians to help understand the origin and use of the cloths and by conservators for whom the species type may have an impact on textile durability, deterioration and hence conservation. However, to date the development of a non-destructive, robust analytical technique has been elusive. This article describes the use of Fourier transform infrared spectroscopy with attenuated total reflection (ATR-FTIR) and principal component analysis (PCA) todifferentiation between historic barkcloths. Three distinct groups of historic cloths were identified using PCA of the FTIR region between 1200 and 1600 cm−1 where molecular vibrations associated with tannins and lignins are dominant. Analysis of contemporary cloths only identified Pipturus albidus cloth as different and highlighted the difficulties around producing a representative textile sample to mimic the historic cloths. While the methodology does not itself identify species, the use of historically well-provenanced samples allows cloths showing similarities to group together and is a significant aid to identification.

Monitoring the interaction of biomolecules is important, and the use of energy transfer is a principal technique in elucidating nanoscale interactions. Lanthanide compounds are promising luminescent probes for biological samples as their emission is longer-lived than any native autofluorescence. Polyoxometalates (POMs) are interesting structural motifs to incorporate lanthanides, offering low toxicity and a size pertinent for biological applications. Here, we employ iso-structured POMs containing either terbium or europium and assess their interaction with serum albumin by sensitisation of a fluorescent tag on the protein via LRET (luminescence resonance energy transfer) by exciting the lanthanide. Time-resolved measurements showed energy transfer with an efficiency of over 90 % for the POM–protein systems. The Tb–POM results were relatively straightforward, while those with the iso-structured Eu–POM were complicated by the effect of protein shielding from the aqueous environment.

The viability of Saccharomyces cerevisiae in biocompatible polymers under different growth conditions and studied using time-resolved fluorescence techniques is presented. Two fluorophores, the viscosity sensitive probe 4-(4-(dimethylamino)styryl)-N-methyl-pyridiniumiodine (DASPMI) and the yeast viability stain 2-chloro-4-(2,3-dihydro-3-methyl-(benzo-1,3-thiazol-2-yl)-methylidene)-1-phenylquinolinium iodide (FUN-1) are used to elucidate information on the incorporated yeast cell viability. Variations in cell viscosity, which are indicative of the cell state, were obtained using DASPMI. Prior to observing FUN-1 in yeast cells using fluorescence lifetime imaging, its photophysics in solution and heterogeneous media were investigated. Time-resolved emission spectra were measured and analysed to associate lifetimes to the spectral emission. Preliminary results show that monitoring the fluorescence lifetime of FUN-1 may give a useful insight into cellular metabolism. The results indicate that both fluorophores may be used to monitor the entrapped yeast cell viability, which is important for in vitro studies and applications, such as that in the biofuel industry, where Saccharomyces cerevisiae are required to remain active in high ethanol environments.

Arrays of nanoantennas consisting of plasmonic dipole pairs have been widely used in surface-enhanced Raman spectroscopy (SERS). Fine-tuned structures that can efficiently convert incident electromagnetic energy to excite molecules and provide enhanced detection. However, this tuning mechanism also has its disadvantages. In order to prevent the cross coupling, the distance between each individual element must be increased. This leads to low packing density values which in turn results in a reduction of the overall enhanced Raman signal when these structures are compared to broadly tuned aggregates of particles such as those obtained through metal sputtering or colloidal deposition. In this work we demonstrate through simulations and experimental work that it is possible to increase the reflected signal of an array of nanoantennas by reducing the distance between them in the direction both perpendicular and parallel to the orientation of the incident electric field. It is shown the resonant wavelength shifts in two different spectral directions depending in how the intercell distance was reduced. These resultant shifts can reduce the tuning capabilities of the structures but also can increase the SERS intensity due to close coupling of the dipole pairs. We believe that these results will enable the design and fabrication of structures possessing a greater degree of tunability together with an overall enhanced Raman signal that can rival aggregated SERS substrates.

Simple to manufacture polysaccharide films containing a silver salt, from which silver nanostructures can be produced in situ by light irradiation, were investigated for possible biosensing applications. The silver nanostructures were patterned in situ within a film and cast from a liquid solution of gellan gum, using a compact time-resolved fluorescence microscope. The position and time of irradiation, made using a semiconductor laser in CW mode, were computer controlled. Evidence for their formation was obtained via UV-vis spectroscopy, AFM and SEM-EDAX. On drying the polysaccharide film exhibited a viscosity increase of several orders of magnitude, which was elucidated by changes in the fluorescence lifetime of a probe molecule (DASPMI). To demonstrate the potential for biocompatible sensing applications the influence of the presence of areas of silver nanostructures on the fluorescence of a protein (bovine serum albumin) labelled with fluorescein isothiocyanate was monitored via fluorescence lifetime imaging and the photophysical behaviour found to be consistent with a metal induced increase in the radiative decay rate.

Mixed silica-calcite matrices were prepared by developing a "low" temperature (sol-gel) method in presence of several biocompatible polymers, thus providing samples with adequate porosity for the flow of biological fluids and also mechanically robust. In order to analyse and characterise the sample's microenvironments, the highly solvatochromic probe Nile red was used, which enabled the role of polymer addition upon local environmental effects in the host media to be elucidated. The polymers used were polyethylene glycol, polymethylmethacrylate and polyethylene. Each matrix was also characterized with respect to microstructure, morphology and pore size via the use of X-ray diffractometry and scanning electron microscopy. The results show that is was possible to obtain, in a controlled way, mixed silica-calcite matrices with a wide range of porosities (important if the material is to be used for scaffold or drug release applications, for example). The spectroscopic behaviour of Nile red when incorporated has confirmed the existence of distinct and specific local polarities within each type of matrix that may determine to a large extent the mechanism of interaction between these matrices and biological molecules.

Metamaterials are being increasingly used as highly sensitive detection devices. The design of these structures and the ability to effect changes in response through small changes in the geometry of their constituent elements allow for the enhancement of known analysis techniques such as infrared or Raman spectroscopy. High electromagnetic fields have been shown to occur in features such as small gaps and sharp tips and these so called “hot-spots” are the main focus of recent work in Surface Enhanced Raman Spectroscopy (SERS). Previous work has shown dipole pairs with small gaps between them to be suitable for the SERS detection of very small amounts of organic compounds. The main difficulties lie in the small dimensions (≤100 nm) necessary to attain a significant response at the typical Raman pump wavelengths. Also the small size of the gaps is a challenge when it comes to prevent “bridging” between the structures during the fabrication process. In this work we show, through simulations, that carefully controlling the length of dipolar structures as well as the gap between these dipoles a resonant response can be achieved close to the pump Raman wavelengths. Also, we see that increasing the width of the dipole pair shifts the resonant peaks to longer wavelengths. By optimizing their geometry, more efficient and easier to fabricate structures can be used as environmental organic sensors.

Fast response optical sensors for oxygen, based on luminescent electropolymerised porphyrin polymers, are described. The sensitivity of the electropolymerised polymers for oxygen detection was found to be dependent on the potential at which the polymers were formed. Results are presented for polymers formed at two different oxidation potentials and for two platinum porphyrins: Pt tetraphenylporphyrin (Pt-TPP) and Pt octaethylporphyrin (Pt-OEP). Sensitivities of the poly-Pt-TPP and poly-Pt-OEP films to dissolved oxygen, given by the Stern–Volmer quenching coefficients, were obtained from luminescence lifetime measurements and were 1.12 (mg l–1)–1 and 2.07 (mg l–1)–1, respectively. The response time, which was determined from luminescence intensity measurements, for the poly-Pt-OEP to a step change in oxygen concentration of 4.3 mg l–1 to 38.6 mg l–1 was 8 ms. The limit of detection obtained for the Pt-OEP based sensor was 0.06 mg l–1.

The efficiency of Fcrster resonance energy transfer (FRET) can be enhanced in the presence of a metal. Herein, we demonstrate the increased efficiency for a novel model sensor system where FRET is shown to occur between Rhodamine 6G in the bulk sol–gel matrix and Texas Red, which is held a fixed distance away by covalent attachment onto a silane spacer. Silver colloids are formed using light to initiate the reduction of a silver salt, which can be achieved at controlled locations within the film. Both the fluorescence intensity and lifetime maps and analysis indicate that an enhanced FRET efficiency has been achieved in the presence of silver nanoparticles. An increase in efficiency of 1.2–1.5 times is demonstrated depending on the spacer used. The novelty of our approach lies in the method of silver-nanoparticle formation, which allows for the accurate positioning of the silver nanoparticles and hence selective fluorescence enhancement within a biocompatible host material. Our work gives a practical demonstration of metal-enhanced FRET and demonstrates the ability of such systems to be developed for molecular-recognition applications that could find use in lab-on-a-chip technologies.

Fluorescence microscopy provides a non-invasive means for visualising dynamic protein interactions. As well as allowing the calculation of kinetic processes via the use of time-resolved fluorescence, localisation of the protein within cells or model systems can be monitored. These fluorescence lifetime images (FLIM) have become the preferred technique for elucidating protein dynamics due to the fact that the fluorescence lifetime is an absolute measure, in the main independent of fluorophore concentration and intensity fluctuations caused by factors such as photobleaching. In this work we demonstrate the use of a time-resolved fluorescence microscopy, employing a high repetition rate laser excitation source applied to study the influence of a metal surface on fluorescence tagged protein and to elucidate viscosity using the fluorescence lifetime probe DASPMI. These were studied in a cellular environment (yeast) and in a model system based on a sol-gel derived material, in which silver nanostructures were formed in situ using irradiation from a semiconductor laser in CW mode incorporated on a compact time-resolved fluorescence microscope (HORIBA Scientific DeltaDiode and DynaMyc).

The presence of a conducting metal surface is known to affect the emission of a fluorophore in its proximity. This can lead to an enhancement in its fluorescence intensity along with a decrease in the fluorescence lifetime. This phenomenon, sometimes known as metal enhanced fluorescence, has implications in the area of sensing and “lab on a chip” applications. Here controlled, localised use of metallic structures can be advantageous in enhancing the detection of a fluorescent signal. The sol–gel technique has been demonstrated as a useful method by which to produce a biocompatible material. The versatility of the reaction allows for the inclusion of metal ions, which can form metallic nanostructures permitting the potential enhancement of fluorescence to be exhibited. In this work we incorporate silver nitrate within silica sol–gel derived films produced using a simple procedure at relative low temperatures (close to ambient). A compact time-resolved fluorescence microscope equipped with a semiconductor laser was used to photoactivate the silver ions to form localised metallic structures within the films. Patterning was achieved by computer control of the microscope stage and using the laser in CW mode. The films were characterised using AFM and UV-vis spectroscopy to ascertain the presence of the photoactivated silver nanostructures. The effect of the presence of these structures was elucidated by studying the time-resolved fluorescence of FITC labelled bovine serum albumin adsorbed to the films, where a decrease in the lifetime of the FITC label was observed in the location of the nanostructures.

This paper describes a new method for the immoblization of metalloporphyrin molecules for optical oxygen sensing. The porphyrin molecules have an acrylamide group attached allowing the porphyrin indicator to be covalently bound within a hydrogel polymer. Two hydrogel monomers: hydroxyethylmethylacrylamide (HEMA) and acrylamide have been investigated to assess their suitability as host polymers for the porphyrins. The photophysics of both the base and Platinum porphyrin: tetra porphyrin are discussed. Platinum tetra porphyrin bound in a hydrogel polymer using HEMA as the monomer unit was found to have a good sensitivity to oxygen.

A pH optical fibre chemical sensor with 16 sensing points located along a 200µm core PCS fibre is reported. The sensing points are 2 mm in length positioned between 2 m and 72 m apart.