Forensic Discrimination of Drug Powder Based on Drug Mixing Condition Determined Using Micro Fourier Transform Infrared Spectroscopy.

The quantitative evaluation of the drug mixing condition was conducted for application in the forensic discrimination of drug powders using micro Fourier transform infrared (FT-IR) spectroscopy. Bromhexine hydrochloride (BHCl) and p-hydroxybenzoic acid (PHBA) were used as the simulated drug and additive, respectively. Equal masses of two chemicals were (1) simply mixed, (2) homogenized using agate mortar, or (3) dissolved in methanol and dried, and then (4) homogenized using agate mortar. The mixed powders dispersed on BaF2 plates were subjected to mapping analysis of micro FT-IR spectroscopy using synchrotron radiation (SR) or globar light in transmission mode with aperture sizes of 2.5 x 2.5 and 10 x 10µm2, and x-y scanning steps of 2.5 and 10 µm, respectively. The areas of the vibration bands specific to BHCl (C-N bending) and PHBA (C=O stretching) were converted to the molar contents (CBHCl, CPHBA), and the relative content ratio (RCR: CPHBA/[CBHCl + CPHBA]) was used as one mixing parameter. The resulting two-dimensional distribution map provided the relative spatial localizations of the two species, and frequency histograms with a horizontal axis of RCR were plotted to evaluate the RCR distribution. The percentage frequency of the extreme value in which RCR was 0 or 1 (%EV) was used as one mixing index. After excluding the extreme values, the coefficient of variation (CV) of the RCR distribution was used as another mixing index. The differentiation among four mixing modes could be evaluated from the standpoint of %EV and CV, and the discrimination capacity by SR instrument was superior to that by globe light instrument.

Effects of Machine Washing on the Chromatography Parameters of Polyester Fiber Gel Permeation.

Fiber examination is frequently performed in forensics, and gel permeation chromatography (GPC) is one candidate method for discriminating polyester fibers. Here, the effects of machine washing on weight-average molecular weight (M w), polydispersity index (PDI), and the percentage peak area of cyclic ethylene terephthalate trimer (PPAL) of commercial polyester shirts and manufactured poly(ethylene terephthalate) (PET) yarns were investigated using GPC. GPC was performed using a 1,1,1,3,3,3-hexafluoro-propan-2-ol polymer solubilizer, styrene-divinylbenzene copolymer GPC columns, a chloroform mobile phase, and a 254 nm absorbance monitor. The statistical change in the polyester fibers during machine washing was evaluated by comparing three GPC parameters of the same fiber samples before and after machine washing. Among the commercial polyester shirts examined, the GPC parameters changed significantly after machine washing with a considerable PPAL decrease. In contrast, the GPC parameters of manufactured PET yarns changed significantly with a moderate increase in M w. This work elucidates the change on GPC parameters of polyester fibers by machine washing.

Non-destructive analysis of hollow-shaped single fibers using X-ray computed tomography.

A commercial high-resolution X-ray computed tomography (CT) was utilized for non-destructive analysis of single fibers. The micro-CT apparatus was employed because it is applicable to both colored and colorless fibers. A sample preparation using adhesive sheets was demonstrated, and the method is similar to typical tape-lift sample collection method in crime cases. Different cross-sectional shapes of nylon and polyester single fibers were non-destructively distinguished, and the method is applicable to all types of fibers. Cross-sectional areas, aperture ratios, and volumes of individual fibers were directly and automatically measured using the open-source software. The observed parameters were within a coefficient of variation of 3%. In addition, a mass of a single fragment of a fiber can be estimated when the local density is given.

Nondestructive Differentiation of Polyester Single White Fibers Using Synchrotron Radiation Microbeam X-ray Fluorescence Spectrometry with Vertical Focusing.

In this study, the nondestructive differentiation of individual white polyester clothing fibers was accomplished via synchrotron radiation microbeam X-ray fluorescence (SR-µ-XRF) analysis. SR-µ-XRF with vertical focusing is a useful nondestructive method for the analysis of a single polyester clothing fiber. Kirkpatrick-Baez (KB) mirror was used to vertically focus 20 keV X-rays for the analysis of 22 individual white polyester fibers taken from clothing commonly sold in Japan. SR-µ-XRF with a vertical focused 2 µm (V) × 300 µm (H) beam was approximately 12.8 times more sensitive than SR-XRF with an unfocused 300 µm (V) × 300 µm (H) beam for the detection of elements in single fibers. The minimum detection limits (MDLs) of the SR-µ-XRF method were 8.15 ppm for Cl and 0.06 ppm for Br. In addition to Ti in TiO2 delustering agents, Zr and Nb impurities in the delustering agents were detected in individual fibers. Sb from a polymerization catalyst and Co from a transesterification catalyst were also detected in individual fibers. Comparing the Ti Kß /Sb Lα,ß and Zr Kα /Nb Kα X-ray intensity ratios was a useful way to distinguish individual clothing fibers, and 98% of the fibers were differentiated when additional trace elements were used as discrimination indicators.

Direct identification of various copper phthalocyanine pigments in automotive paints and paint smears by laser desorption ionization mass spectrometry.

Direct identification of copper phthalocyanine (CuPc) and chlorinated CuPcs in paints for discrimination between blue automobile paints by means of laser desorption mass spectrometry (LDMS) in the absence of a matrix is reported. The models consisted of eight commercially available CuPc pigments applied to a piece of plain white coating paper. The relationship between the peak intensity at m/z 575 of the CuPc, the number of pulsed laser shots, and laser power was compared to optimize laser abrasion. LDMS analysis of the model paints demonstrated that all characteristic components of the CuPc pigments in the paint films were in good agreement with those in the powder pigments. Further, the chlorinated CuPcs in the paint films could be distinguished. A quantity of 42 blue paint films, representing the paints used for painting Japanese domestic trucks, was examined by LDMS analysis. Results indicate that the paints can be classified into four categories based on the chlorinated CuPc components of the paints. Therefore, LDMS spectra of CuPc pigments would be useful for the identification of paints in forensic investigations. Herein, we report the successful identification of the CuPcs in a paint smear on the frame of a bicycle damaged in a hit-and-run accident, using the LDMS spectra.