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Time‐resolved Raman spectroscopy, spatially offset Raman spectroscopy and time‐resolved spatially offset Raman spectroscopy (TR‐SORS) have proven their capability for the non‐invasive profiling of deep layers of a sample. Recent studies have indicated that TR‐SORS exhibits an enhanced selectivity toward the deep layers of a sample. However, the enhanced depth profiling efficiency of TR‐SORS, in comparison with time‐resolved Raman spectroscopy and spatially offset Raman spectroscopy, is yet to be assessed and explained in accordance to the synergistic effects of spatial and temporal resolutions. This study provides a critical investigation of the depth profiling efficiency of the three deep Raman techniques. The study compares the efficiency of the various deep Raman spectroscopy techniques for the stand‐off detection of explosive precursors hidden in highly fluorescing packaging. The study explains for the first time the synergistic effects of spatial and temporal resolutions in the deep Raman techniques and their impact on the acquired spectral data. Copyright © 2013 John Wiley & Sons, Ltd.

Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for non-invasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than one minute. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers and customs checkpoints.

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 meters under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 seconds of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems.

A time-resolved inverse spatially offset Raman spectrometer was constructed for depth profiling of Raman-active substances under both the lab and the field environments. The system operating principles and performance are discussed along with its advantages relative to traditional continuous wave spatially offset Raman spectrometer. The developed spectrometer uses a combination of space- and time-resolved detection in order to obtain high-quality Raman spectra from substances hidden behind coloured opaque surface layers, such as plastic and garments, with a single measurement. The time-gated spatially offset Raman spectrometer was successfully used to detect concealed explosives and drug precursors under incandescent and fluorescent background light as well as under daylight. The average screening time was 50 s per measurement. The excitation energy requirements were relatively low (20 mW) which makes the probe safe for screening hazardous substances. The unit has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than previous picosecond-based systems, to provide a functional platform for in-line or in-field sensing of chemical substances.

Spatially offset Raman spectroscopy (SORS) is a powerful new technique for the non-invasive detection and identification of concealed substances and drugs. Here, we demonstrate the SORS technique in several scenarios that are relevant to customs screening, postal screening, drug detection and forensics applications. The examples include analysis of a multi-layered postal package to identify a concealed substance; identification of an antibiotic capsule inside its plastic blister pack; analysis of an envelope containing a powder; and identification of a drug dissolved in a clear solvent, contained in a non-transparent plastic bottle. As well as providing practical examples of SORS, the results highlight several considerations regarding the use of SORS in the field, including the advantages of different analysis geometries and the ability to tailor instrument parameters and optics to suit different types of packages and samples. We also discuss the features and benefits of SORS in relation to existing Raman techniques, including confocal microscopy, wide area illumination and the conventional backscattered Raman spectroscopy. The results will contribute to the recognition of SORS as a promising method for the rapid, chemically specific analysis and detection of drugs and pharmaceuticals.

New Zealand chestnuts grow relatively large by comparison with Asian or American varieties and have the potential to be a lucrative crop. However they are susceptible to fungal rots and need to be dried at relatively low temperatures in order to prevent significant spoilage. Drying curves for New Zealand chestnut variety ‘1015’ were obtained at 30 °C, which was the maximum drying temperature that did not cause significant quality degradation. Two distinct falling-rate drying periods were observed: an initial period during which a relatively high drying rate decreased rapidly, followed by a period of lower drying rates which decreased only gradually. The first period most likely corresponded to the time required for the surface region to reach moisture equilibrium, since it was clearly affected by external factors such as air movement and the absence or presence of moisture barrier(s). The second period represented the diffusion-controlled process, and was largely unaffected by external factors. The mean apparent diffusivity of whole chestnuts at 30 °C was 5.1 × 10−11 m2 s−1.

The temperature sensitivities of absorption and reduced scattering coefficients in the range 700-1000 nm are determined for the liquid phantom Intralipid using spatially resolved continuous wave measurements. The measurements were conducted on a 10 L heated volume of 1% Intralipid subjected to a 40-30 degrees C cooling regime. The temperature sensitivities of the absorbance coefficients are similar to that expected for pure water. However, the reduced scattering coefficients are more sensitive than can be explained by temperature related density changes, and show an unexpected relationship with wavelength. We have also found that temperature perturbations provide a useful means to evaluate instrument model performance.

Noninvasive standoff deep Raman spectroscopy has been utilised for the detection of explosives precursors in highly fluorescing packaging from 15 m. To our knowledge this is the first time standoff deep Raman spectroscopy of concealed substances in highly fluorescing coloured packaging is demonstrated. Time-resolved Raman spectroscopy, spatially offset Raman spectroscopy and time-resolved spatially offset Raman spectroscopy have been compared to identify their selectivity towards the deep layers of a sample. The selectivity of time-resolved Raman spectroscopy towards the concealed chemical substances was found to be comparable to that of spatially offset Raman spectroscopy. However, time-resolved Raman spectroscopy did not require precise translation of the laser excitation beam onto the surface of the interrogated packaging as in the case of spatially offset Raman spectroscopy. Our results confirm that standoff time-resolved spatially offset Raman spectroscopy has significantly higher selectivity towards the deep layers of a sample when compared to the other deep Raman spectroscopy modes. The developed spectrometer was capable of detecting the concealed substances within 5 s of data acquisition. By using time-resolved spatially Raman spectroscopy, a Raman spectrum that is representative of the content alone was acquired without the use of sophisticated algorithms to eliminate the spectral contributions of the packaging material within the acquired spectrum as in the case of time-resolved Raman spectroscopy and spatially offset Raman spectroscopy.

In this paper, spatially offset Raman spectroscopy (SORS) is demonstrated for noninvasively investigating the composition of drug mixtures inside an opaque plastic container. The mixtures consisted of three components including a target drug (acetaminophen or phenylephrine hydrochloride) and two diluents (glucose and caffeine). The target drug concentrations ranged from 5% to 100%. After conducting SORS analysis to ascertain the Raman spectra of the concealed mixtures, principal component analysis (PCA) was performed on the SORS spectra to reveal trends within the data. Partial least squares (PLS) regression was used to construct models that predicted the concentration of each target drug, in the presence of the other two diluents. The PLS models were able to predict the concentration of acetaminophen in the validation samples with a root-mean-square error of prediction (RMSEP) of 3.8% and the concentration of phenylephrine hydrochloride with an RMSEP of 4.6%. This work demonstrates the potential of SORS, used in conjunction with multivariate statistical techniques, to perform noninvasive, quantitative analysis on mixtures inside opaque containers. This has applications for pharmaceutical analysis, such as monitoring the degradation of pharmaceutical products on the shelf, in forensic investigations of counterfeit drugs, and for the analysis of illicit drug mixtures which may contain multiple components.

Spatially offset Raman spectroscopy (SORS) is demonstrated for the non-contact detection of energetic materials concealed within non-transparent, diffusely scattering containers. A modified design of an inverse SORS probe has been developed and tested. The SORS probe has been successfully used for the detection of various energetic substances inside different types of plastic containers. The tests have been successfully conducted under incandescent and fluorescent background lights as well as under daylight conditions, using a non-contact working distance of 6 cm. The interrogation times for the detection of the substances were less than 1 minute in each case, highlighting the suitability of the device for near real-time detection of concealed hazards in the field. The device has potential applications in forensic analysis and homeland security investigations.

We present the temperature dependence of absorption and reduced scattering coefficients of 1.8% Intralipid measured by frequency-domain photon-migration spectroscopy between 710 and 850 nm. These measurements were made in the physiologically relevant 30 to 40 degrees C temperature range. The temperature coefficients for absorption were consistent during heating and cooling and follow closely other reported results. The change in absorption coefficient at 740 nm suggests that a minimum temperature change of 4 degrees C is observable within the error limits. We found that the reduced scattering coefficient shows a hysteresis with temperature at 740 nm. The temperature coefficient for reduced scattering determined from heating cycle measurements agrees with theory and other measurements within the error limits.

We present a wavelength-tunable frequency-domain instrument for the characterization of liquid turbid media. The instrument employs a tunable titanium-sapphire laser modulated by an acousto-optic modulator. The absorption and reduced scattering coefficient of Intralipid(R) 20%, diluted to concentrations of 0.94 to 4.00%, are measured over the wavelength range 710 to 850 nm at 10-nm intervals. The standard measurement errors for the absorption and reduced scattering coefficients are 1 and 2.5%, respectively. Extrapolation to 0% Intralipid(R) concentration gives an absorption coefficient that closely follows that of water, overestimating the absorption of pure water by less than 10%. The reduced scattering coefficient is compared at 750 nm with published results and is found consistent within the experimental error. We compare the reduced scattering coefficient to an estimate based on Mie theory and find the reduced scattering coefficient underestimated the Mie theory result by about 9%.

Techniques are presented for enhancing weak Raman scattering signals for rapid yet accurate substance detection. Novel surfaces that allow signal enhancement quantification are described as are eye-safe methodologies that maximize the stand-off Raman detection range.

Accuracy and precision are typically among the most important factors in the design of an optical measurement system for quantitative assay of natural products. Often the variation expected in the constituent and absorber of interest is small—perhaps less than 20% of the mean as for soluble-solid concentration in Kiwifruit, for example. Most natural products in their raw form are not pure absorbers: they also scatter light. This complicates the measurement problem as scatter can introduce variation far greater than the absorption we are trying to measure.