Sensitivity enhancement and fringe reduction in tunable diode laser spectroscopy using hemispherical diffusers.

The use of diffuse, highly reflective optical components, in particular, a hemispherical BaSO4 diffuser, at the point of light injection into non-transparent or turbid media was evaluated as a means to increase the measurement sensitivity of spectroscopic absorption measurements. By performing the light injection from, e.g., an optical fiber through a component designed to make the light diffuse and to reflect (and thereby re-inject) light scattered from the sample, the total amount of light delivered into the sample is increased. Further, the occurrence of possible interference fringes is strongly reduced.

Frequency-modulated light scattering interferometry employed for optical properties and dynamics studies of turbid media.

In the present work, fiber-based frequency-modulated light scattering interferometry (FMLSI) is developed and employed for studies of optical properties and dynamics in liquid phantoms made from Intralipid(®). The fiber-based FMLSI system retrieves the optical properties by examining the intensity fluctuations through the turbid medium in a heterodyne detection scheme using a continuous-wave frequency-modulated coherent light source. A time resolution of 21 ps is obtained, and the experimental results for the diluted Intralipid phantoms show good agreement with the predicted results based on published data. The present system shows great potential for assessment of optical properties as well as dynamic studies in liquid phantoms, dairy products, and human tissues.

Laser absorption spectroscopy of oxygen confined in highly porous hollow sphere xerogel.

An Al2O3 xerogel with a distinctive microstructure is studied for the application of laser absorption spectroscopy of oxygen. The xerogel has an exceptionally high porosity (up to 88%) and a large pore size (up to 3.6 µm). Using the method of gas-in-scattering media absorption spectroscopy (GASMAS), a long optical path length (about 3.5m) and high enhancement factor (over 300 times) are achieved as the result of extremely strong multiple-scattering when the light is transmitted through the air-filled, hollow-sphere alumina xerogel. We investigate how the micro-physical feature influences the optical property. As part of the optical sensing system, the material's gas exchange dynamics are also experimentally studied.

Pathlength determination for gas in scattering media absorption spectroscopy.

Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique.

Noninvasive monitoring of gas in the lungs and intestines of newborn infants using diode lasers: feasibility study.

Preterm newborn infants have a high morbidity rate. The most frequently affected organs where free gas is involved are the lungs and intestines. In respiratory distress syndrome, both hyperexpanded and atelectatic (collapsed) areas occur, and in necrotizing enterocolitis, intramural gas may appear in the intestine. Today, these conditions are diagnosed with x-ray radiography. A bed-side, rapid, nonintrusive, and gas-specific technique for in vivo gas sensing would improve diagnosis. We report the use of noninvasive laser spectroscopy, for the first time, to assess gas content in the lungs and intestines of three full-term infants. Water vapor and oxygen were studied with two low-power diode lasers, illuminating the skin and detecting light a few centimeters away. Water vapor was easily detected in the intestines and was also observed in the lungs. The relatively thick chest walls of the infants prevented detection of the weaker oxygen signal in this study. However, results from a previous phantom study, together with scaling of the results presented here to the typical chest-wall thickness of preterm infants, suggest that oxygen also should be detectable in their lungs.

Detection of elemental mercury by multimode diode laser correlation spectroscopy.

We demonstrate a method for elemental mercury detection based on correlation spectroscopy employing UV laser radiation generated by sum-frequency mixing of two visible multimode diode lasers. Resonance matching of the multimode UV laser is achieved in a wide wavelength range and with good tolerance for various operating conditions. Large mode-hops provide an off-resonance baseline, eliminating interferences from other gas species with broadband absorption. A sensitivity of 1 µg/m3 is obtained for a 1-m path length and 30-s integration time. The performance of the system shows promise for mercury monitoring in industrial applications.

Tea classification and quality assessment using laser-induced fluorescence and chemometric evaluation.

Laser-induced fluorescence was used to evaluate the classification and quality of Chinese oolong teas and jasmine teas. The fluorescence of four different types of Chinese oolong teas-Guangdong oolong, North Fujian oolong, South Fujian oolong, and Taiwan oolong was recorded and singular value decomposition was used to describe the autofluoresence of the tea samples. Linear discriminant analysis was used to train a predictive chemometric model and a leave-one-out methodology was used to classify the types and evaluate the quality of the tea samples. The predicted classification of the oolong teas and the grade of the jasmine teas were estimated using this method. The agreement between the grades evaluated by the tea experts and by the chemometric model shows the potential of this technique to be used for practical assessment of tea grades.

Gas spectroscopy and optical path-length assessment in scattering media using a frequency-modulated continuous-wave diode laser.

Simultaneous assessment of the spectroscopic absorption signal of gas enclosed in a scattering medium and the corresponding optical path length of the probing light is demonstrated using a single setup. Sensitive gas absorption measurements are performed by a tunable diode laser using wavelength-modulation spectroscopy, while the path length is evaluated by the frequency-modulated cw technique commonly used in the field of telecommunication. Proof-of-principle measurements are demonstrated with water vapor as the absorbing gas and using polystyrene foam as an inhomogeneously scattering medium. The combination of these techniques opens up new possibilities for straightforward evaluation of gas presence and exchange in scattering media.

Using 915 nm laser excited Tm³+/Er³+/Ho³+- doped NaYbF4 upconversion nanoparticles for in vitro and deeper in vivo bioimaging without overheating irradiation.

Successful further development of superhigh-constrast upconversion (UC) bioimaging requires addressing the existing paradox: 980 nm laser light is used to excite upconversion nanoparticles (UCNPs), while 980 nm light has strong optical absorption of water and biological specimens. The overheating caused by 980 nm excitation laser light in UC bioimaging is computationally and experimentally investigated for the first time. A new promising excitation approach for better near-infrared to near-infrared (NIR-to-NIR) UC photoluminescence in vitro or in vivo imaging is proposed employing a cost-effective 915 nm laser. This novel laser excitation method provides drastically less heating of the biological specimen and larger imaging depth in the animals or tissues due to quite low water absorption. Experimentally obtained thermal-graphic maps of the mouse in response to the laser heating are investigated to demonstrate the less heating advantage of the 915 nm laser. Our tissue phantom experiments and simulations verified that the 915 nm laser is superior to the 980 nm laser for deep tissue imaging. A novel and facile strategy for surface functionalization is utilized to render UCNPs hydrophilic, stable, and cell targeting. These as-prepared UCNPs were characterized by TEM, emission spectroscopy, XRD, FTIR, and zeta potential. Specifically targeting UCNPs excited with a 915 nm laser have shown very high contrast UC bioimaging. Highly stable DSPE-mPEG-5000-encapsulated UCNPs were injected into mice to perform in vivo imaging. Imaging and spectroscopy analysis of UC photoluminescence demonstrated that a 915 nm laser can serve as a new promising excitation light for UC animal imaging.

Near vacuum ultraviolet luminescence of Gd3+ and Er3+ ions generated by super saturation upconversion processes.

Near vacuum ultraviolet (UV) upconversion (UC) emissions with a spectral resolution of 1 nm, from the (6)G(J), (6)D(J), (6)I(J), (6)P(J) levels of Gd(3+) and the (2)L(17/2), (4)D(7/2), (2)H(2)(9/2), (2)D(5/2), (4)G(7/2), (2)K(13/2), (2)P(3/2) levels of Er(3+), were observed under 974 nm laser excitation. Mechanism analyses illustrate that successive energy transfers (ETs) from Yb(3+) to Er(3+) generate UV UC radiations in Er(3+), while two resonant ETs from Er(3+) to Gd(3+) lead to UV UC radiations in Gd(3+). Power dependence analyses indicate that the expected inefficient four- and five-photon processes have been switched into efficient two-photon processes due to a super saturation UC phenomenon that employs consecutive saturations at the intermediate states.

Upconversion emission tuning from green to red in Yb3+/Ho3+-codoped NaYF4 nanocrystals by tridoping with Ce3+ ions.

Upconversion (UC) emission tuning from green to red in monodisperse NaYF(4):Yb(3+)/Ho(3+) nanocrystals was successfully achieved by tridoping with Ce(3+) ions under diode laser excitation of 970 nm. It is proposed that two efficient cross-relaxation processes, 5S2/5F4(Ho) + 2F(5/2)(Ce) --> 5F5(Ho) + 2F(7/2)(Ce) and 5I6(Ho) + 2F(5/2)(Ce) --> 5I7(Ho) + 2F(7/2)(Ce)between Ho(3+) and Ce(3+) ions, have been employed to select UC pathways to tune the UC radiation. Theoretical investigations based on steady-state equations demonstrate the proposed UC mechanisms and explain well the observed linear increase of the UC red-to-green intensity ratio with the increment of Ce(3+) ion concentrations.

Oxygen measurement by multimode diode lasers employing gas correlation spectroscopy.

Multimode diode laser (MDL)-based correlation spectroscopy (COSPEC) was used to measure oxygen in ambient air, thereby employing a diode laser (DL) having an emission spectrum that overlaps the oxygen absorption lines of the A band. A sensitivity of 700 ppm m was achieved with good accuracy (2%) and linearity (R(2)=0.999). For comparison, measurements of ambient oxygen were also performed by tunable DL absorption spectroscopy (TDLAS) technique employing a vertical cavity surface emitting laser. We demonstrate that, despite slightly degraded sensitivity, the MDL-based COSPEC-based oxygen sensor has the advantages of high stability, low cost, ease-of-use, and relaxed requirements in component selection and instrument buildup compared with the TDLAS-based instrument.

Gas detection by correlation spectroscopy employing a multimode diode laser.

A gas sensor based on the gas-correlation technique has been developed using a multimode diode laser (MDL) in a dual-beam detection scheme. Measurement of CO(2) mixed with CO as an interfering gas is successfully demonstrated using a 1570 nm tunable MDL. Despite overlapping absorption spectra and occasional mode hops, the interfering signals can be effectively excluded by a statistical procedure including correlation analysis and outlier identification. The gas concentration is retrieved from several pair-correlated signals by a linear-regression scheme, yielding a reliable and accurate measurement. This demonstrates the utility of the unsophisticated MDLs as novel light sources for gas detection applications.

Broadband spectroscopic sensor for real-time monitoring of industrial SO(2) emissions.

A spectroscopic system for continuous real-time monitoring of SO(2) concentrations in industrial emissions was developed. The sensor is well suited for field applications due to simple and compact instrumental design, and robust data evaluation based on ultraviolet broadband absorption without the use of any calibration cell. The sensor has a detection limit of 1 ppm, and was employed both for gas-flow simulations with and without suspended particles, and for in situ measurement of SO(2) concentrations in the flue gas emitted from an industrial coal-fired boiler. The price/performance ratio of the instrument is expected to be superior to other comparable real-time monitoring systems.

Long-path monitoring of NO2 with a 635 nm diode laser using frequency-modulation spectroscopy.

In situ monitoring of traffic-generated nitrogen dioxide (NO2) emissions using long-path absorption spectroscopy is reported. High-sensitivity detection of NO2 is achieved by employing two-tone frequency-modulation spectroscopy at a visible absorption band using a tunable high-power diode laser operated around 635 nm. A real-time absorption spectrometer is accomplished by repetitively applying a rectangular current pulse to the diode-laser operating current, allowing detection of isolated NO2 absorption lines. A detection limit of 10 microg/m3 for NO2 at atmospheric pressure using a 160 m absorption path is demonstrated. Continuous monitoring of NO2 over a road intersection at peak traffic is performed.

Concentration measurement of gas embedded in scattering media by employing absorption and time-resolved laser spectroscopy.

Diode-laser-based absorption spectroscopy for the evaluation of embedded gas concentrations in porous materials is demonstrated in measurements of molecular oxygen dispersed throughout scattering polystyrene foam, used here as a generic test material. The mean path length of light scattered in the material is determined with the temporal characteristics of the radiation transmitted through the sample. This combined with sensitive gas-absorption measurements employing wavelength-modulation spectroscopy yields an oxygen concentration in polystyrene foam of 20.4% corresponding to a foam porosity of 98%, which is consistent with manufacturing specifications. This feasibility study opens many possibilities for quantitative measurements by using the method of gas-in-scattering-media absorption spectroscopy.