Time-resolved spectral-domain optical coherence tomography with CMOS SPAD sensors.

We present a first spectral-domain optical coherence tomography (SD-OCT) system deploying a complementary metal-oxide-semiconductor (CMOS) single-photon avalanche diode (SPAD) based, time-resolved line sensor. The sensor with 1024 pixels achieves a sensitivity of 87 dB at an A-scan rate of 1 kHz using a supercontinuum laser source with a repetition rate of 20 MHz, 38 nm bandwidth, and 2 mW power at 850 nm centre wavelength. In the time-resolved mode of the sensor, the system combines low-coherence interferometry (LCI) and massively parallel time-resolved single-photon counting to control the detection of interference spectra on the single-photon level based on the time-of-arrival of photons. For proof of concept demonstration of the combined detection scheme we show the acquisition of time-resolved interference spectra and the reconstruction of OCT images from selected time bins. Then, we exemplify the temporal discrimination feature with 50 ps time resolution and 249 ps timing uncertainty by removing unwanted reflections from along the optical path at a 30 mm distance from the sample. The current limitations of the proposed technique in terms of sensor parameters are analysed and potential improvements are identified for advanced photonic applications.

pH sensing through a single optical fibre using SERS and CMOS SPAD line arrays.

Full exploitation of fibre Raman probes has been limited by the obstruction of weak Raman signals by background fluorescence of the sample and the intrinsic Raman signal of the delivery fibre. Here we utilised functionalised gold nanoshells (NS) to take advantage of the surface-enhanced Raman spectroscopy (SERS) effect to enhance the pH responsive spectrum of 4-mercaptobenzoic acid (MBA). However, the fibre background is still dominant. Using the photon arrival time-resolving capability of a CMOS single-photon avalanche diode (SPAD) based line sensor, we recover the SERS spectrum without a fibre background in a 10 s measurement. In this manner, pH sensing through a multimode fibre at a low excitation power that is safe for future in vivo applications, with short acquisition times (10 or 60 s), is demonstrated. A measurement precision of ± 0.07 pH units is thus achieved.

Time-resolved spectroscopy at 19,000 lines per second using a CMOS SPAD line array enables advanced biophotonics applications.

A SPAD-based line sensor fabricated in 130 nm CMOS technology capable of acquiring time-resolved fluorescence spectra (TRFS) in 8.3 milliseconds is presented. To the best of our knowledge, this is the fastest time correlated single photon counting (TCSPC) TRFS acquisition reported to date. The line sensor is an upgrade to our prior work and incorporates: i) parallelized interface from sensor to surrounding circuitry enabling high line rate to the PC (19,000 lines/s) and ii) novel time-gating architecture where detected photons in the OFF region are rejected digitally after the output stage of the SPAD. The time-gating architecture was chosen to avoid electrical transients on the SPAD high voltage supplies when gating is achieved by excess bias modulation. The time-gate has an adjustable location and time window width allowing the user to focus on time-events of interest. On-chip integrated center-of-mass (CMM) calculations provide efficient acquisition of photon arrivals and direct lifetime estimation of fluorescence decays. Furthermore, any of the SPC, TCSPC and on-chip CMM modes can be used in conjunction with the time-gating. The higher readout rate and versatile architecture greatly empower the user and will allow widespread applications across many techniques and disciplines. Here we focused on 3 examples of TRFS and time-gated Raman spectroscopy: i) kinetics of chlorophyll A fluorescence from an intact leaf; ii) kinetics of a thrombin biosensor FRET probe from quenched to fluorescence states; iii) ex vivo mouse lung tissue autofluorescence TRFS; iv) time-gated Raman spectroscopy of toluene at 3056 cm-1 peak. To the best of our knowledge, we detect spectrally for the first time the fast rise in fluorescence lifetime of chlorophyll A in a measurement over single fluorescent transient.

Preparation and characterization TiO(x)-Pt/C catalyst for hydrogen oxidation reaction.

The hydrogen oxidation reaction (HOR) was studied at the home made TiO(x)-Pt/C nanocatalysts in 0.5 mol dm(-3) HClO(4) at 25 degrees C. Pt/C catalyst was first synthesized by modified ethylene glycol method (EG) on commercially used carbon support (Vulcan XC-72). Then TiO(x)-Pt/C catalyst was prepared by the polyole method followed by TiO(x) post-deposition. The synthesized catalyst was characterized by XRD, TEM and EDX techniques. It was found that Pt/C catalyst nanoparticles were homogenously distributed over carbon support with the mean particle size of about 2.4 nm. The quite similar, homogenous distribution and particle size were obtained for Pt/C doped by TiO(x) catalyst which was the confirmation that TiO(x) post-deposition did not lead to significant growth of the Pt nanoparticles. The electrochemically active surface area of the catalyst was determined by using the cyclic voltammetry technique.The kinetics of hydrogen oxidation was investigated by the linear sweep voltammetry technique at the rotating disc electrode (RDE). The kinetic equations used for the analysis were derived considering the reversible or irreversible nature of the kinetics of the HOR. It was found that the hydrogen oxidation reaction for an investigated catalyst proceeded as an electrochemically reversible reaction. The values determined for the kinetic parameters-Tafel slope of 28 mV dec(-1) and exchange current density about 0.4 mA cm(-2)(Pt) are in good agreement with usually reported values for a hydrogen oxidation reaction with platinum catalysts in acid solutions.

Dosimetry of the microSelectron-HDR Ir-192 source using PRESAGE and optical CT.

Optical CT, using a solid polyurethane (PRESAGE) radiochromic dosimeter, has been used to evaluate dose distributions produced by the microSelectron-HDR Ir-192 source. The anisotropy functions obtained through optical CT are in good agreement with Monte Carlo and previously published results especially at polar angle above 20 degrees. The results indicated an evident potential for using solid polymer dosimetry as an accurate method for 3-D dosimetry, although refinements to the existing methods are necessary before the technique can be used clinically.

A preliminary analysis of LET effects in the dosimetry of proton beams using PRESAGE and optical CT.

PRESAGE is a solid dosimeter based on a clear polyurethane matrix doped with radiochromic components (leuco dyes). On exposure to ionizing radiation a colour change is generated in the dosimeter, and hence an optical absorption or optical density change that can be read out by optical CT. The main focus of present investigations has been to investigate the possible LET dependence of PRESAGE to the dose deposited at the Bragg maxima using proton beam absorbed dose measurements, and the linearity of response of the dosimeter. Proton irradiations were performed using the proton beam facility at the Douglas Cyclotron, Clatterbridge Centre for Oncology (CCO) using a configuration that approximates the one routinely used in treatment of patients with ocular tumours. The samples were irradiated with both monoenergetic and modulated proton beams. Optical tomography measurements were carried out with our in-house CCD-based optical-CT system. Initial results for monoenergetic beams show that in PRESAGE the measured ratio of the Bragg peak dose to entrance dose is approximately 2:1 whereas the true value measured at CCO is approximately 5:1. For range-modulated proton beams, the absorbed dose close to the end of the proton range, i.e. at the Bragg peak, is underestimated by approximately 20% compared to the corresponding diode measurement. Further investigations are necessary to understand and quantify the effect of LET on PRESAGE, and to measure the uncertainties related to our optical CT.

Composite hypo-hyper-d-intermetallic and interionic phases as supported interactive electrocatalysts.

Interactive, strong interbonding and highly electron conductive nonstoichiometric titanium suboxide catalytic supports, Magneli phases (Ti(n)O(2n-1), on average Ti(4)O(7)), have been used in the electrocatalysis of hydrogen (HELR) and oxygen (OELR) electrode reactions with remarkable consequences and advanced achievements. The theory of hypo-hyper-d-interelectronic bonding of transition metal ions and atoms has been employed for selective ordered grafting and shown to stay in the core of the strong metal-support interaction (SMSI) in heterogeneous catalysis and electrocatalysis, and thereby the substantial cause for the improved synergistic activity of composite (electro)catalysts. The same fundament has been the thermodynamic basis for the thermal production of symmetric intermetallic Laves type phases of nanostructured electrocatalysts, in particular the ones with higher oxophilic properties of hypo-d-elements. Remarkably advanced in electrocatalytic activity, highly monatomically dispersed deposits of Pt upon Magneli phases are shown to be unique and highly promising electrocatalysts for the cathodic oxygen reduction (ORR). Nanostructured Au upon a thin nanocrystalline film of anatase titania has been confirmed by X-ray photoelectron spectroscopy (XPS) as a typical classical paradigm of the SMSI, and at the same time affording the basis for gold with strained d-orbitals, as the reversible hydrogen electrode. Magneli phases have been shown to be the best electrocatalytic supports with unique properties both for low temperature PEM fuel cells (LT PEM FCs) with pronounced CO tolerance and water electrolysis in membrane type hydrogen generators.