Toward the Required Detection Limits for Volatile Organic Constituents in Marine Environments with Infrared Evanescent Field Chemical Sensors.

A portable sensor system for the simultaneous detection of multiple environmentally relevant volatile organic compounds (VOCs) in real seawater based on Fourier transform infrared fiber-optic evanescent wave spectroscopy (FT-IR-FEWS) was developed. A cylindrical silver halide (AgX) fiber with an ethylene/propylene copolymer (E/P-co) coated flattened segment was used as an active optical transducer. The polymer membrane enriches the hydrophobic analytes, while water is effectively excluded from the penetration depth of the evanescent field. Determination of multicomponent mixtures (i.e., 10 VOCs in real-world seawater samples) collected in Arcachon Bay, France revealed a high accuracy and reproducibility with detection limits down to 560 ppb. The measurement showed no significant influence from changing water conditions (e.g., salinity, turbidity, and temperature or other interfering substances). The time constants for 90% saturation of the polymer ranged from 20 to 60 min. The sensor system is capable of being transported for on-site monitoring of environmental pollutants in aqueous matrices with efficient long-term stability, thus showing great potential to be utilized as an early warning system.

Using Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR) spectroscopy to distinguish between melanoma cells with a different metastatic potential.

The vast majority of cancer related deaths are caused by metastatic tumors. Therefore, identifying the metastatic potential of cancer cells is of great importance both for prognosis and for determining the correct treatment. Infrared (IR) spectroscopy of biological cells is an evolving research area, whose main aim is to find the spectral differences between diseased and healthy cells. In the present study, we demonstrate that Attenuated Total Reflection Fourier Transform IR (ATR-FTIR) spectroscopy may be used to determine the metastatic potential of cancer cells. Using the ATR-FTIR spectroscopy, we can identify spectral alterations that are a result of hydration or molecular changes. We examined two murine melanoma cells with a common genetic background but a different metastatic level, and similarly, two human melanoma cells. Our findings revealed that higher metastatic potential correlates with membrane hydration level. Measuring the spectral properties of the cells allows us to determine the membrane hydration levels. Thus, ATR-FTIR spectroscopy has the potential to help in cancer metastasis prognosis.

Fourier transform infrared spectroscopy on external perturbations inducing secondary structure changes of hemoglobin.

The secondary structure of proteins and their conformation are intimately related to their biological functions. In this study, heat-induced changes in the secondary structure and conformation of hemoglobin were investigated via infrared attenuated total reflection (IR-ATR) spectroscopy. The secondary structure changes of hemoglobin were derived from IR-ATR spectra using second derivatives and curve fitting. Thereby, the thermal denaturation temperature ranges and the secondary structure changes with temperature were revealed. More detailed information on the secondary structure and conformation was elucidated via two-dimensional infrared correlation spectroscopy. This study deciphers the detailed conformational behavior of hemoglobin molecular changes along with temperature, and creates a general methodological framework for analyzing the heat-induced behavior of biomacromolecules.

High-sensitivity infrared attenuated total reflectance sensors for in situ multicomponent detection of volatile organic compounds in water.

In situ detection of volatile organic compounds (VOCs) in aqueous environments is imperative for ensuring the quality and safety of water supplies, yet it remains a challenging analytical task. We present a high-sensitivity method for in situ analysis of multicomponent VOCs at low concentrations based on the use of infrared attenuated total reflection (IR-ATR) spectroscopy. This protocol uses a unique ATR waveguide, which comprises a planar silver halide (AgCl(x)Br(1-x)) fiber with cylindrical extensions at both ends to increase the number of internal reflections, and a polymer coating that traps VOCs and excludes water molecules. Depending on the type of VOC and measurement scenario, IR spectra with specific frequency windows, scan times and spectral resolutions are obtained, from which concentration information is derived. This protocol allows simultaneous detection of multiple VOCs at concentrations around 10 p.p.b., and it enables accurate quantification via a single measurement within 5 min without the need for sample collection or sample pretreatment. This IR-ATR sensor technology will be useful for other applications; we have included a procedure for the analysis of protein conformation changes in Supplementary Methods as an example.

Probing the secondary structure of bovine serum albumin during heat-induced denaturation using mid-infrared fiberoptic sensors.

Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy using a special waveguide based on a silver halide fiber was used for probing the heat-induced secondary structure and conformation changes of bovine serum albumin (BSA). From the secondary derivative and the curve fitting of the obtained ATR-FTIR spectra, the changes of the BSA secondary structure with temperature were clearly identified. Two different thermal denaturation temperature ranges (i.e., 50-52 and 80-82 °C, at which a change of the protein structure occurred) were determined, while only one denaturation temperature was previously identified via classical FTIR measurements. Additionally, taking advantage of two-dimensional correlation spectroscopy more detailed information on changes of the protein secondary structure was revealed. The developed method facilitates in situ, sensitive, and more in-depth probing of protein secondary structures, which represents a significant advancement compared to conventional characterization methods.

Mid-infrared planar silver halide waveguides with integrated grating couplers.

Grating couplers for planar silver halide waveguides were designed and fabricated by using focused ion beam (FIB) milling technology, facilitating coupling of mid-infrared radiation from quantum cascade lasers into thin-film waveguide structures. An optimized rectangular grating structure for an emitted wavelength of 10.4 µm, with a grating constant of 16.4 µm was integrated into a silver halide waveguide substrate via an optimized FIB fabrication procedure. Efficient incoupling and radiation propagation through the waveguide was confirmed by analyzing droplets of acetic acid at different concentrations, deposited at the waveguide surface via evanescent field absorption spectroscopy.

Determination of chlorinated hydrocarbons in water using highly sensitive mid-infrared sensor technology.

Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring.

The investigation of water diffusion into teflon copolymer revealed by fiber-optic evanescent wave spectroscopy.

Fiber-optic evanescent wave infrared spectroscopy was used for the study of water diffusion in Teflon and has provided valuable information about the structure of water in amorphous hydrophobic polymers. Time-dependent absorption measurements were carried out in two spectral ranges: 3000-3800 cm(-1), associated with the O-H stretching mode, and 1620-1670 cm(-1), associated with the H-O-H bending mode of water. The results indicate that the IR spectra could be expressed as a superposition of spectra due to two species of water molecules: strongly and weakly hydrogen-bonded. We suggest that water molecules form clusters with strongly hydrogen-bonded molecules at the cores and with weakly hydrogen-bonded molecules at the external parts of the clusters. A mathematical model, based on a linear diffusion equation with a moving boundary, gave a ratio of 3.5 between the total number of molecules in a cluster and the number of water molecules at the core of the cluster.

Mid-infrared fiber-optic attenuated total reflection spectroscopy of the solid-liquid phase transition of water.

Measurements of mid-infrared (MIR) absorption spectra of water and heavy water were carried out by fiber-optic evanescent wave spectroscopy, using silver halide (AgClBr) infrared fibers. Such measurements were performed for the first time on one sample, during the solid-liquid phase transition. From the variation of the spectra with temperature we found a new isosbestic point (at 3280 cm(-1) for H(2)O or at 2475 cm(-1) for D(2)O) and we identified five components of the O-H (O-D) stretch band. These phenomena have provided new information about the molecular structure of water.

Fiberoptic infrared spectroscopy: a novel tool for the analysis of urine and urinary salts in situ and in real time.

OBJECTIVES: To use infrared fiberoptic spectroscopy for the analysis of urinary salts in real time and with no sample processing; and to assess the practical role of this method for the quantitative measurement of the composition of urine and for the diagnosis of urolithiasis in patients. METHODS: Urine samples were obtained from two groups of patients: 24 patients with stone formation after shock wave lithotripsy and 24 normal subjects of similar age. Infrared absorption measurements were performed in real time, using infrared transmitting silver halide fibers. The absorption data were compared with the infrared absorption spectra of aqueous solutions prepared in our laboratory, with known concentrations of known urinary salts. The results were used for the study of the chemical composition of these salts in the urine samples and for a quantitative analysis of the concentration of the salts. RESULTS: We determined the composition of the stones in 20 of the 24 patients on the basis of the characteristic absorption peaks for the oxalates, carbonates, urates, and phosphates observed in their urinary samples. Using the method mentioned above, we found the concentration of different salts in urine with an average error of 20%. CONCLUSIONS: Fiberoptic infrared spectroscopy could be used as a new diagnostic tool for detecting different urinary salts in urine, finding their chemical composition, and determining their concentrations, without any sample preparation.