Hugues Tariel

Chalcogenide optical fibers for mid-infrared sensing

Abstract. Chalcogenide glasses are a matchless material as far as mid-infrared (IR) applications are concerned. They transmit light typically from 2 to 12 μm and even as far as 20 μm depending on their composition, and numerous glass compositions can be designed for optical fibers. One of the most promising applications of these fibers consists in implementing fiber evanescent wave spectroscopy, which enables detection of the mid-IR signature of most biomolecules. The principles of fiber evanescent wave spectroscopy are recalled together with the benefit of using selenide glass to carry out this spectroscopy. Then, two large-scale studies in recent years in medicine and food safety are exposed. To conclude, the future strategy is presented. It focuses on the development of rare earth-doped fibers used as mid-IR sources on one hand and tellurium-based glasses to shift the limit of detection toward longer wavelength on the other hand.

Shaping of looped miniaturized chalcogenide fiber sensing heads for mid-infrared sensing.

Chalcogenide glass fibers are promising photonic tools to develop Fiber Evanescent Wave Spectroscopy (FEWS) optical sensors working in the mid-infrared region. Numerous pioneering works have already been carried out showing their efficiency, especially for bio-medical applications. Nevertheless, this technology remains confined to academic studies at the laboratory scale because chalcogenide glass fibers are difficult to shape to produce reliable, sensitive and compact sensors. In this paper, a new method for designing and fabricating a compact and robust sensing head with a selenide glass fiber is described. Compact looped sensing heads with diameter equal to 2 mm were thus shaped. This represents an outstanding achievement considering the brittleness of such uncoated fibers. FEWS experiments were implemented using alcoholic solutions as target samples showing that the sensitivity is higher than with the routinely used classical fiber. It is also shown that the best compromise in term of sensitivity is to fabricate a sensing head including two full loops. From a mechanical point of view, the breaking loads of the loop shaped head are also much higher than with classical fiber. Finally, this achievement paves the way for the use of mid-infrared technology during in situ and even in vivo medical operations. Indeed, is is now possible to slide a chalcogenide glass fiber in the operating channel of a standard 2.8 mm diameter catheter.

Mid-infrared spectroscopy of serum, a promising non-invasive method to assess prognosis in patients with ascites and cirrhosis

Background & aims Prognostic tests are critical in the management of patients with cirrhosis and ascites. Biological tests or scores perform poorly in that situation. Mid-infrared fibre evanescent wave spectroscopy (MIR-FEWS) which allows for global serum metabolic profiling may provide more relevant information by measuring a wider range of metabolic parameters in serum. Here we present the accuracy of a MIR-FEWS based predictive model for the prognosis of 6 months survival in patients with ascites and cirrhosis. Methods Patients with ascites were prospectively included and followed up for 6 months. MIR-FEWS spectra were measured in serum samples. The most informative spectral variables obtained by MIR-FEWS were selected by FADA algorithm and then used to build the MIR model. Accuracy of this model was assessed by ROC curves and 90%/10% Monte Carlo cross-validation. MIR model accuracy for 6 months survival was compared to that of the Child-Pugh and MELD scores. Results 119 patients were included. The mean age was 57.36±13.70, the MELD score was 16.32±6.26, and the Child-Pugh score was 9.5±1.83. During follow-up, 23 patients died (20%). The MIR model had an AUROC for 6 months mortality of 0.90 (CI95: 0.88–0.91), the MELD 0.77 (CI95: 0.66–0.89) and Child-Pugh 0.76 (CI95: 0.66–0.88). MELD and Child-Pugh AUROCs were significantly lower than that of the MIR model (p = 0.02 and p = 0.02 respectively). Multivariate logistic regression analysis showed that MELD (p<0.05, OR:0.86;CI95:0.76–0.97), Beta blockers (p = 0.036;OR:0.20;CI95:0.04–0.90), and the MIR model (p<0.001; OR:0.50; CI95:0.37–0.66), were significantly associated with 6 months mortality. Conclusions In this pilot study MIR-FEWS more accurately assess the 6-month prognosis of patients with ascites and cirrhosis than the MELD or Child-Pugh scores. These promising results, if confirmed by a larger study, suggest that mid infrared spectroscopy could be helpful in the management of these patients.

Development of optical fibers for mid-infrared sensing: state of the art and recent achievements

Chalcogenide glass fibers are matchless devices to collect mi-infrared signal. Depending on the spectroscopic strategy, different kind of optical fibers have been developed during the past 10 years. The first fibers have been fabricated from selenide glasses to implement Fiber Evanescent Wave Spectroscopy (FEWS). It is an efficient way to collect optical spectra in situ, in real time and even, in the future, in vivo. Thanks to selenide glass fibers, it is possible to record such spectra on the mid-infrared range from 2 to 11 μm. This working window gives access to the fundamental vibration band of most of biological molecules and numerous multi-disciplinary works have been led in biology and medicine. New glasses, only based on tellurium, have been recently developed, initially in the frame of the Darwin mission led by the European Space Agency (ESA). These glasses transmit light further toward the farinfrared and permit to reach the absorption band of CO2 located at 15 μm as requested by the ESA. Moreover, these telluride glass fiber are also very interesting for FEWS and medical application. Indeed, they give access to the mid-infrared signal of biomolecules beyond 11 μm, where classical selenide glass fibers are blind. Alternatively, in order to fight against global warning, some optical fibers have been developed for the monitoring of the CO2 stored into geological storage area underground. These fibers were doped with Dy3+ which emits a broad fluorescent band embedding the CO2 absorption band at 4.3 μm. thus, these fibers are used both to transmit light and as secondary sources in the mid-infrared. To conclude, original microstructurated fibers have also been used for mid-infrared sensing. They exhibit a nice sensitivity compared to classical chalcogenide glass fibers.

Selenide and telluride glasses for mid-infrared bio-sensing

Fiber Evanescent Wave Spectroscopy (FEWS) is an efficient way to collect optical spectra in situ, in real time and even, hopefully, in vivo. Thanks to selenide glass fibers, it is possible to get such spectra over the whole mid-infrared range from 2 to 12 μm. This working window gives access to the fundamental vibration band of most of biological molecules. Moreover selenide glasses are stable and easy to handle, and it is possible to shape the fiber and create a tapered sensing head to drastically increase the sensitivity. Within the past decades, numerous multi-disciplinary studies have been conducted in collaboration with the City Hospital of Rennes. Clinical trials have provided very promising results in biology and medicine which have led to the creation in 2011 of the DIAFIR Company dedicated to the commercialization of fiber-based infrared biosensors. In addition, new glasses based on tellurium only have been recently developed, initially in the framework of the Darwin mission led by the European Space Agency (ESA). These glasses transmit light further into the far-infrared and could also be very useful for medical applications in the near future. Indeed, they permit to reach the vibrational bands of biomolecules laying from 12 to 16 μm where selenide glasses do not transmit light anymore. However, while Se is a very good glass former, telluride glasses tend to crystallize easily due to the metallic nature of Te bonds. Hence, further work is under way to stabilize the glass composition for fibers drawing and to lower the optical losses for improving their sensitivity as bio-sensors.