An integrated optical Bragg grating refractometer for volatile organic compound detection

We report an integrated optical Bragg grating detector, fabricated using a direct UV-writing approach, that when coated with a thin-film of a hydrophobic siloxane co-polymer can perform as an all-optically accessed detector for hydrocarbon vapour. Upon exposure to a series of organic solvent vapours, both negative and positive Bragg wavelength shifts of differing magnitudes were measured. This was attributed to a combination of swelling and/or hydrocarbon solvent filling the free volume within the polymer film. A quantitative structural property relationship (QSPR) approach was utilised to create a multiple variable linear regression model, built from parameters that chemically described the hydrocarbons and the intermolecular interactions present between the co-polymer and hydrocarbon molecules. The resulting linear regression model indicated that the degree of swelling of the polysiloxane thin film when exposed to vapours of different hydrocarbons was due to the physico-chemical properties of the hydrocarbons and that this was the main causative factor of the measured Bragg wavelength shifts. Furthermore, this linear regression model allows for the prediction of the Bragg wavelength shift that would be measured upon exposure to vapours of another defined hydrocarbon. This detector is intrinsically safe in flammable environments. It includes on-chip thermal compensation, operates at telecoms wavelengths and has a predictable response to a variety of hydrocarbons making it ideal for detection of flammable hydrocarbon vapours in industrial and domestic processes

Light harvesting in silicon(111) surfaces using covalently attached protoporphyrin IX dyes

We report the photosensitization of crystalline silicon via energy transfer using covalently attached protoporphyrin IX (PpIX) derivative molecules at different distances via changing the diol linker to the surface. The diol linker molecule chain length was varied from 2 carbon to 10 carbon lengths in order to change the distance of PpIX to the Si(111) surface between 6 A and 18 A. Fluorescence quenching as a function of the PpIX-Si surface distance showed a decrease in the fluorescence lifetime by almost two orders of magnitude at the closest separation. The experimental fluorescence lifetimes are explained theoretically by a classical Chance-Prock-Silbey model. At a separation below 2 nm, we observe for the first time, a Forster like dipole-dipole energy transfer with a characteristic distance of R-o = 2.7 nm

Twist-bend nematics, liquid crystal dimers, structure–property relations

<p>One of the current challenges in liquid crystal science is to understand the molecular factors leading to the formation of the intriguing twist-bend nematic phase (N_TB) and determine its properties. During our earlier hunt for the N_TB phase created on cooling directly from the isotropic phase and not the nematic phase, we had prepared 30 symmetric liquid crystal dimers. These had odd spacers and methylene links to the two mesogenic groups; desirable but clearly not essential features for the formation of the N_TB. Here, we report the phases that the dimers exhibit and their transition temperatures as functions of both the lengths of the spacer and the terminal chains. In addition we describe the transitional entropies, their optical textures, the X-ray scattering patterns and the ²H NMR spectra employed in characterising the phases. All of which may lead to important properties of the twist-bend nematic phase.</p

Surface Modifications by Field Induced Diffusion

By applying a voltage pulse to a scanning tunneling microscope tip the surface under the tip will be modified. We have in this paper taken a closer look at the model of electric field induced surface diffusion of adatoms including the van der Waals force as a contribution in formations of a mound on a surface. The dipole moment of an adatom is the sum of the surface induced dipole moment (which is constant) and the dipole moment due to electric field polarisation which depends on the strength and polarity of the electric field. The electric field is analytically modelled by a point charge over an infinite conducting flat surface. From this we calculate the force that cause adatoms to migrate. The calculated force is small for voltage used, typical 1 pN, but due to thermal vibration adatoms are hopping on the surface and even a small net force can be significant in the drift of adatoms. In this way we obtain a novel formula for a polarity dependent threshold voltage for mound formation on the surface for positive tip. Knowing the voltage of the pulse we then can calculate the radius of the formed mound. A threshold electric field for mound formation of about 2 V/nm is calculated. In addition, we found that van der Waals force is of importance for shorter distances and its contribution to the radial force on the adatoms has to be considered for distances smaller than 1.5 nm for commonly used voltages

Breath Analysis Using Laser Spectroscopic Techniques: Breath Biomarkers, Spectral Fingerprints, and Detection Limits

Breath analysis, a promising new field of medicine and medical instrumentation, potentially offers noninvasive, real-time, and point-of-care (POC) disease diagnostics and metabolic status monitoring. Numerous breath biomarkers have been detected and quantified so far by using the GC-MS technique. Recent advances in laser spectroscopic techniques and laser sources have driven breath analysis to new heights, moving from laboratory research to commercial reality. Laser spectroscopic detection techniques not only have high-sensitivity and high-selectivity, as equivalently offered by the MS-based techniques, but also have the advantageous features of near real-time response, low instrument costs, and POC function. Of the approximately 35 established breath biomarkers, such as acetone, ammonia, carbon dioxide, ethane, methane, and nitric oxide, 14 species in exhaled human breath have been analyzed by high-sensitivity laser spectroscopic techniques, namely, tunable diode laser absorption spectroscopy (TDLAS), cavity ringdown spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS), cavity enhanced absorption spectroscopy (CEAS), cavity leak-out spectroscopy (CALOS), photoacoustic spectroscopy (PAS), quartz-enhanced photoacoustic spectroscopy (QEPAS), and optical frequency comb cavity-enhanced absorption spectroscopy (OFC-CEAS). Spectral fingerprints of the measured biomarkers span from the UV to the mid-IR spectral regions and the detection limits achieved by the laser techniques range from parts per million to parts per billion levels. Sensors using the laser spectroscopic techniques for a few breath biomarkers, e.g., carbon dioxide, nitric oxide, etc. are commercially available. This review presents an update on the latest developments in laser-based breath analysis

Supramolecular approaches to molecular machines

The chapter provides an overview of the use of functional supramolecular assemblies for the creation of molecular-scale mcahine-like device

Tracking a photo-switchable surface-localised supramolecular interaction via refractive index

As supramolecular chemistry evolves, from the design of interactions in the solution and the solid state to applications at surfaces, there is a need for the development of analytical techniques capable of directly interrogating surface-localised supramolecular interactions. We present a proof-of-concept integrated optical Bragg grating sensor, capable of evanescently detecting small changes in refractive index at infrared wavelengths within a microfluidic system. The high spectral fidelity of the Bragg gratings combined with precise thermal compensation enables direct monitoring of the surface throughout the experiment, enabling the sensor to probe changes in situ and in real-time during surface preparation and chemical modification, and then to follow the progress of a dynamic surface-localised supramolecular interaction. In this study the sensor is assessed through the investigation of a photo-switchable inclusion complex between an azobenzene-functionalised surface and cyclodextrin in aqueous solution. The ability to investigate supramolecular interactions directly in real-time upon a planar surface via refractive index offers a valuable new tool in the understanding of complex dynamic supramolecular systems.</span

Self-assembly into infinite tapes by 2,7-disubstituted-1,8-naphthyridines in the solid state

2,7-Disubstituted-1,8-naphthyridine derivatives have been found to self-assemble into infinite 1-D tapes in the solid state in a manner similar to that seen previously for their 2,6-disubstituted pyridine analogues.<br/