Four novel alkyl 2-cyanoacylate monomers and their use in latent fingermark detection by mid-infrared spectral imaging.

Four novel alkyl 2-cyanoacrylate monomers (alkyl=1-cyanoethyl, 2-cyanoethyl, trideuteromethyl and pentadeuteroethyl) have been tested for their ability to develop latent fingermarks that can then be visualized using mid-infrared spectral (chemical) imaging. Each of the four monomers was chosen for its potential to produce a strong, isolated infrared spectral band in its corresponding polymer (to provide spectral contrast against most backgrounds), as well as for its potential ability to be fumed onto fingermarks in the manner of conventional ethyl 2-cyanoacrylate (superglue). With the exception of the 2-cyanoethyl 2-cyanoacrylate, which had to be fumed under reduced pressure, all of the monomers were found to be sufficiently volatile to be fumed in a conventional fuming cabinet. All four monomers polymerized selectively on fingermark ridges on a variety of non-porous and semi-porous surfaces, leading to excellent development of the fingermarks. Unfortunately, although high quality mid-infrared spectral images of the fingermarks could be formed for all of the polymers at various frequencies, the new CN or CD stretching vibrations did not give rise to strong enough absorption intensities for good contrast on difficult backgrounds such as polymer banknotes. However, in the 1-cyanoethyl 2-cyanoacrylate polymer, the presence of the additional nitrile group had the unintended but desirable effect of shifting the strong CO absorption to higher frequencies, moving it away from interfering banknote absorptions. This enabled fingermark contrast to be achieved even against the intaglio printing on the banknotes.

Thermal development of latent fingermarks on porous surfaces--further observations and refinements.

In a further study of the thermal development of fingermarks on paper and similar surfaces, it is demonstrated that direct contact heating of the substrate using coated or ceramic surfaces at temperatures in excess of 230°C produces results superior to those obtained using hot air. Fingermarks can also be developed in this way on other cellulose-based substrates such as wood and cotton fabric, though ridge detail is difficult to obtain in the latter case. Fluorescence spectroscopy indicates that the phenomena observed during the thermal development of fingermarks can be reproduced simply by heating untreated white copy paper or filter paper, or these papers treated with solutions of sodium chloride or alanine. There is no evidence to suggest that the observed fluorescence of fingermarks heated on paper is due to a reaction of fingermark constituents on or with the paper. Instead, we maintain that the ridge contrast observed first as fluorescence, and later as brown charring, is simply an acceleration of the thermal degradation of the paper. Thermal degradation of cellulose, a major constituent of paper and wood, is known to give rise to a fluorescent product if sufficient oxygen is available [1-5]. However, the absence of atmospheric oxygen has only a slight effect on the thermal development of fingermarks, indicating that there is sufficient oxygen already present in paper to allow the formation of the fluorescent and charred products. In a depletion study comparing thermal development of fingermarks on paper with development using ninhydrin, the thermal technique was found to be as sensitive as ninhydrin for six out of seven donors. When thermal development was used in sequence with ninhydrin and DFO, it was found that only fingermarks that had been developed to the fluorescent stage (a few seconds of heating) could subsequently be developed with the other reagents. In the reverse sequence, no useful further development was noted for fingermarks that were treated thermally after having been developed with ninhydrin or DFO. Aged fingermarks, including marks from 1-year-old university examination papers were successfully developed using the thermal technique.

Classification of heterogeneous solids using infrared hyperspectral imaging.

Methods were explored for the classification of heterogeneous powder mixtures using Fourier transform infrared (FT-IR) hyperspectral image data. The images collected were non-congruent, meaning that samples of the same mixture do not have the same spatial arrangements of their components in their images. In order to classify such images on a one-image-per-object basis, dimension reduction was carried out so as to produce a score or feature vector for each image that preserved information about the heterogeneity of the sample. These feature vectors were then classified using discriminant analysis (DA) or soft independent modeling of class analogy (SIMCA). The most successful approach was the use of a median-interquartile range "super-spectrum" as the feature vector representing each image; using principal component analysis (PCA) DA classification, 87.5% of training samples were correctly classified using leave-one-out cross-validation, and 100% of a test set were correctly classified. This compares with 52.5% and 72%, respectively, when single-point spectra were used to classify the samples.

Revisiting the thermal development of latent fingerprints on porous surfaces: new aspects and refinements.

Although the ability to develop latent fingerprints on paper using heat alone has been noted previously, it has been considered impractical for casework and inferior to other techniques. Here a new refinement of the technique is demonstrated for the high quality development of latent fingerprints on porous surfaces such as paper. Fingerprints deposited on various papers were developed by exposing them to hot air with a temperature in the vicinity of 300 degrees C, for periods of c. 10-20 sec. Several different heating methods were tested. The novel observation was made that after shorter heating times, fluorescent prints could be observed. These became visible after longer heating times, as noted by earlier workers, but with greatly improved contrast compared with their results. Prints from various donors (and aged prints) were developed with excellent ridge contrast. Direct heating methods (such as with a hot plate or press) produced inferior results. The refined technique, which is simple, safe and inexpensive compared with conventional methods, has great potential for use in forensic laboratories.

An examination of the sequence of intersecting lines using attenuated total reflectance-Fourier transform infrared spectral imaging.

In this study, the potential of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectral imaging as a technique to determine the sequence of line crossings was examined. The technique was successful in determining the sequence of heterogeneous line intersections produced using ballpoint pens and laser printers. By imaging at characteristic frequencies, it was possible to form spectral images showing the spatial distribution of the materials. By examining the spectral images from the inks, it was possible to determine whether the ink was above or below the toner. In blind testing, ATR-FTIR spectral imaging results were directly compared to those obtained by eight experienced forensic document examiners using methods regularly employed in casework. ATR-FTIR spectral imaging was shown to achieve a 100% success rate in the blind tests, whereas some incorrect sequence determinations were made by the forensic document examiners when using traditional techniques. The technique was unable to image ink-jet printing, gel pens, roller ball pens, and felt-tip pens, and was also unable to determine the sequence of intersecting ballpoint pen lines.

The application of infrared chemical imaging to the detection and enhancement of latent fingerprints: method optimization and further findings.

Fourier transform infrared (FTIR) chemical imaging allows the collection of fingerprint images from backgrounds that have traditionally posed problems for conventional fingerprint detection methods. In this work, the suitability of this technique for the imaging of fingerprints on a wider range of difficult surfaces (including polymer banknotes, various types of paper, and aluminum drink cans) has been tested. For each new surface, a systematic methodology was employed to optimize settings such as spectral resolution, number of scans, and pixel aggregation in order to reduce collection time and file-size without compromising spatial resolution and the quality of the final fingerprint image. The imaging of cyanoacrylate-fumed fingerprints on polymer banknotes has been improved, with shorter collection times for larger image areas. One-month-old fingerprints on polymer banknotes have been successfully fumed and imaged. It was also found that FTIR chemical imaging gives high quality images of cyanoacrylate-fumed fingerprints on aluminum drink cans, regardless of the printed background. Although visible and UV light sources do not yield fingerprint images of the same quality on difficult, nonporous backgrounds, in many cases they can be used to locate a fingerprint prior to higher quality imaging by the FTIR technique. Attempts to acquire FTIR images of fingerprints on paper-based porous surfaces that had been treated with established reagents such as ninhydrin were all unsuccessful due to the swamping effect of the cellulose constituents of the paper.

Forensic analysis of bicomponent fibers using infrared chemical imaging.

The application of infrared chemical imaging to the analysis of bicomponent fibers was evaluated. Eleven nominally bicomponent fibers were examined either side-on or in cross-section. In six of the 11 samples, infrared chemical imaging was able to spatially resolve two spectroscopically distinct regions when the fibers were examined side-on. As well as yielding characteristic infrared spectra of each component, the technique also provided images that clearly illustrated the side-by-side configuration of these components in the fiber. In one case it was possible to prepare and image a cross-section of the fiber, but in general the preparation of fiber cross-sections proved very difficult. In five of the 11 samples, the infrared spectra could be used to identify the overall chemical composition of the fibers, according to a published classification scheme, but the fiber components could not be spatially resolved. Difficulties that are inherent to conventional "single-point" infrared spectroscopy, such as interference fringing and sloping baselines, particularly when analyzing acrylic type fibers, were also encountered in the infrared chemical image analysis of bicomponent fibers. A number of infrared sampling techniques were investigated to overcome these problems, and recommendations for the best sampling technique are given. Chemical imaging results were compared with those obtained using conventional fiber microscopy techniques.

Forensic applications of infrared chemical imaging: multi-layered paint chips.

This paper examines the potential of infrared chemical (hyperspectral) imaging as a technique for the forensic analysis of automotive paint chips in particular, and multicomponent (e.g., layered) samples in general. Improved sample preparation procedures for the infrared analysis of paint chips are detailed, with the recommendation that where mounting resins are chemically incompatible with the sample, it is better to mount and section the sample in a soft wax from which the sections can be removed and pressed into a KBr disk for transmission analysis. Infrared chemical images of multilayered paint chips have been successfully obtained, with the chief advantage over conventional infrared analysis being that thousands of infrared spectra are collected in a few minutes across the whole sample, at a spatial resolution of around 5 microm. As with conventional infrared spectroscopy, chemical species can be identified from their spectra, but the wealth of information available can be also extracted in a number of different ways that make multicomponent spectral (and hence chemical) comparisons between two samples easy to visualize and understand. In one approach, the infrared chemical images of two paint chips being compared side-by-side can be viewed as a "movie," in which each frame is an intensity map of the two samples at a given wavenumber (frequency) value. In another approach, the spectra (pixels) in the image files are classified into chemically similar groups, resulting in a "cluster" image that makes it possible to simultaneously compare all of the layers in two paint chips. These methods are applicable to other multicomponent samples, and also to other chemical imaging techniques.

The detection and enhancement of latent fingermarks using infrared chemical imaging.

The use of a new technique, Fourier transform infrared (FTIR) chemical imaging, has been demonstrated for the enhancement of latent fingermarks on a number of surfaces. Images of untreated fingermarks on glass backgrounds with excellent ridge detail were acquired using infrared chemical imaging. High quality fingermarks on glass backgrounds were also developed using ethyl cyanoacrylate (super glue) fuming and subsequent infrared chemical imaging. This new method allows the collection of images from backgrounds that traditionally pose problems for current fingermark detection methods. The background may, for example, be highly colored, have a complex pattern, or possess other pattern or image characteristics that make it difficult to separate fingermark ridges using traditional optical or luminescent visualization. One background that has proven to be a challenging surface for the development of latent fingermarks is the Australian polymer banknote. To demonstrate the power and applicability of infrared chemical imaging, fingermarks fumed with ethyl cyanoacrylate were successfully imaged from Australian polymer banknotes.