应用FTIR光谱技术推断死亡时间

目的 应用傅立叶变换红外(FTIR)光谱技术分析大鼠死后组织、人体离体组织随死亡时间推移的化学降解过程,为死亡时间推断的研究提供新的途径与方法.方法 大鼠断颈处死后置于4℃、20℃、30℃环境,在不同死亡时间点提取大鼠不同组织;收集有同样死亡时间的人尸体组织,离体取材,并运用FFIR光谱仪测定不同化学基团随死后和离体后...     

Source Determination of Red Gel Pen Inks using Raman Spectroscopy and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy combined with Pearson's Product Moment Correlation Coefficients and Principal Component Analysis

The potential combination of two nondestructive techniques, that is, Raman spectroscopy (RS) and attenuated total reflectance–fourier transform infrared (ATR‐FTIR) spectroscopy with Pearson's product moment correlation (PPMC) coefficient (r) and principal component analysis (PCA) to determine the actual source of red gel pen ink used to write a simulated threatening note, was examined. Eighteen (18) red gel pens purchased from Japan and Malaysia from November to December 2014 where one of the pens was used to write a simulated threatening note were analyzed using RS and ATR‐FTIR spectroscopy, respectively. The spectra of all the red gel pen inks including the ink deposited on the simulated threatening note gathered from the RS and ATR‐FTIR analyses were subjected to PPMC coefficient (r) calculation and principal component analysis (PCA). The coefficients r = 0.9985 and r = 0.9912 for pairwise combination of RS and ATR‐FTIR spectra respectively and similarities in terms of PC1 and PC2 scores of one of the inks to the ink deposited on the simulated threatening note substantiated the feasibility of combining RS and ATR‐FTIR spectroscopy with PPMC coefficient (r) and PCA for successful source determination of red gel pen inks. The development of pigment spectral library had allowed the ink deposited on the threatening note to be identified as XSL Poppy Red (CI Pigment Red 112).     

实验性大鼠弥漫性轴索损伤的傅里叶红外光谱检测

目的探讨利用傅里叶红外光谱技术诊断弥漫性轴索损伤的可行性。方法利用HE染色、银染和β-APP免疫组化染色确认大鼠弥漫性轴索损伤模型,利用傅里叶变换显微红外光谱面扫描成像技术检测弥漫性轴索损伤区域酰胺Ⅱ带的光谱分布情况,得到弥漫性轴索损伤的红外光谱数据,绘制红外光谱病理图像。结果实验组与对照组的酰胺Ⅱ带红外光谱吸收度之间存在明显差异,红外光谱病理图像中酰胺Ⅱ带的高吸收区与弥漫性轴索损伤区符合。结论傅里叶红外光谱技术可对弥漫性轴索损伤进行病理形态学诊断。     

Evaluation of shooting distance by AFM and FTIR/ATR analysis of GSR

The techniques of atomic force microscopy (AFM) and Fourier transform infrared attenuated total reflectance (FTIR/ATR) spectroscopy are applied to the analysis of gun-shot residue (GSR) to test their ability to determine shooting distance and discrimination of the powder manufacturers. AFM is a nondestructive technique that is capable of characterizing the shapes and size distributions of GSR particles with resolution down to less than a nanometer. This may be useful for estimation of the shooting distance. Our AFM images of GSR show that the size distribution of the particles is inversely proportional to the shooting distance. Discrimination of powder manufacturers is tested by FTIR/ATR investigation of GSR. Identifying the specific compounds in the GSR by FTIR/ATR was not possible because it is a mixture of the debris of several compounds that compose the residue. However, it is shown that the GSR from different cartridges has characteristic FTIR/ATR bands that may be useful in differentiating the powder manufacturers. It appears promising that the development of AFM and FTIR/ATR databases for various powder manufacturers may be useful in analysis and identification of GSR.     

Application of Micro‐Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy to Ink Examination in Signatures Written with Ballpoint Pen on Questioned Documents

Questioned documents examined in a forensic laboratory sometimes contain signatures written with ballpoint pen inks; these signatures were examined to assess the feasibility of micro‐attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy as a forensic tool. Micro‐ATR FTIR spectra for signatures written with 63 ballpoint pens available commercially in Korea were obtained and used to construct an FTIR spectral database. A library‐searching program was utilized to identify the manufacturer, blend, and model of each black ballpoint pen ink based upon their FTIR peak intensities, positions, and patterns in the spectral database. This FTIR technique was also successfully used in determining the sequence of homogeneous line intersections from the crossing lines of two ballpoint pen signatures. We have demonstrated with a set of sample documents that micro‐ATR FTIR is a viable nondestructive analytical method that can be used to identify the origin of the ballpoint pen ink used to mark signatures.     

An Analysis of Systematic Elemental Changes in Decomposing Bone

The aim of this pilot study was to investigate compositional changes in bone during decomposition. Elemental concentrations of barium, calcium, iron, potassium, magnesium, zinc and phosphorus in porcine bone (as an experimental analog for human bone) were analyzed by inductively coupled plasma optical emission spectroscopy (ICP‐OES). The samples were taken from porcine bone subjected to shallow burial and surface depositions at 28‐day intervals for a period of 140 days. Results indicated that ICP‐OES elemental profiling has potential to be developed as a forensic test for determining whether a bone sample originates from the early stages of soft tissue putrefaction. Significant changes in iron, sodium and potassium concentrations were found over 140 days. These elements are known to be primarily associated with proteins and/or tissue fluids within the bone. Changes in their respective concentrations may therefore be linked to dehydration over time and in turn may be indicative of time since deposition.     

Application of Volume‐of‐Fluid Method to Analyze the Viscosity Effect on the Spine Formation of Bloodstains

In bloodstain pattern analysis, the blood droplet volume and surface impact velocity play an important role, and many related experimental studies have been carried out. If an appropriate computational fluid dynamics (CFD) model that could solve bloodstain patterns, especially spine formation bloodstain patterns, can be obtained, the blood droplet volume and impact speeds at various crime scenes can be predicted more accurately. For this purpose, Flow‐3D software using the volume‐of‐fluid method was applied to analyze the behavior of human blood droplets during an impact event, especially focusing on the viscous effect on splashing, which forms the spine which can be used to predict the impact velocity. To obtain a non‐Newtonian viscosity model of blood for a computational fluid dynamic analysis, the venous blood samples of 163 people were tested using a hemorheology instrument. Among the venous blood samples of 163 people, 37 samples for which all blood test results were in a normal range were selected for the non‐Newtonian viscosity modeling. From the CFD analysis, it could be concluded that a non‐Newtonian viscosity model is more appropriate than a constant viscosity model for predicting splashing that forms the spine. The gradient of the non‐Newtonian model at a high shear rate has more of an effect on spine formation than that at a low shear rate. The lowest viscosity with a high velocity at the outer front of the radiating flow plays an important role in forming the splashing pattern.     

Determination of Time since Death using Vitreous Humor Tryptophan

Determination of time since death (TSD) plays very important role in forensic examination as it narrows down field of suspects and aids in deceased identification. This study utilizes the fluorescence property of vitreous humor (VH) tryptophan to determine TSD using o‐phthalaldehyde (OPA). The detection limit of these fluorometric studies was found to be 8 ppb indicating sensitivity and high accuracy in TSD determination. The study was performed on selected 76 cadaver with known TSD ranging from 3 to 90 h. Excellent correlation between VH tryptophan and TSD was obtained with a coefficient of correlation R² = 0.9590. Results showed statistically significant increase in vitreous tryptophan with TSD up to 90 h, and the proposed method was efficaciously applied for prediction of TSD as no systematic error exist. The regression equation obtained from the study is [Trp] = 2.21 + 2.98 * TSD.     

Characterization of Printing Inks Using DART‐Q‐TOF‐MS and Attenuated Total Reflectance (ATR) FTIR

The rise in improved and widely accessible printing technology has resulted in an interest to develop rapid and minimally destructive chemical analytical techniques that can characterize printing inks for forensic document analysis. Chemical characterization of printing inks allows for both discrimination of inks originating from different sources and the association of inks originating from the same source. Direct analysis in real‐time mass spectrometry (DART‐MS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) were used in tandem to analyze four different classes of printing inks: inkjets, toners, offset, and intaglio. A total of 319 samples or ~ 80 samples from each class were analyzed directly on a paper substrate using the two methods. DART‐MS was found to characterize the semi‐volatile polymeric vehicle components, while ATR‐FTIR provided chemical information associated with the bulk components of these inks. Complimentary data results in improved discrimination when both techniques are used in succession resulting in >96% discrimination for all toners, 95% for all inkjets, >92% for all offset, and >54% for all intaglio inks.     

The Morphology of Fecal and Regurgitation Artifacts Deposited by the Blow Fly Lucilia cuprina Fed a Diet of Human Blood

Fly feces and regurgitation deposits may be mistaken for bloodstain patterns at a crime scene, potentially compromising event reconstruction and/or misdirecting police resources. In some instances, these artifacts contain sufficient human biological material to generate a full DNA profile, sometimes 2 years after deposition. Clearly, it is important that investigators can make the distinction between artifacts and bloodstains. This study examined 6645 artifacts deposited on a smooth, nonporous surface after Lucilia cuprina were fed human blood. Artifacts were also compared with bloodstains on a variety of other surfaces. Both similarities and differences were found between artifacts and bloodstains, highlighting the need for an identification system to assist personnel with little training in bloodstain pattern analysis. The morphology of the artifacts has been described so that these deposits may be more clearly distinguished from bloodstains, targeted by crime scene personnel as potential sources of human DNA, and/or identified as potential evidence contaminants. Flowcharts have been devised to facilitate the analysis.     

二次溅落状血迹形态的模拟实验观察

目的观察二次溅落状血迹的形态特征,探讨其形成机理及与行为方式的关系。方法建立室内现场环境,用10mL血液,以单滴连续滴落或一次性倾倒方式,从10～160 cm高度以10 cm为间隔,制作二次溅落状血迹模型;用棍棒打击及撞击方式制作低位打击及头部撞击溅落血迹模型。观察各种血迹分布,并分析比较其形态差异。结果二次溅落状血迹和头部撞击溅落状血迹在垂直面上均形成倒三角形空白区域的分布形态,但前者分布面积较后者小;低位打击溅落在垂直面上的血迹无此特征,且打击飞溅血滴的飞行角度大于二次溅落血迹。结论利用二次溅落状血迹的形态特征,对于鉴别低位溅血、分析行为方式、证实相关证词具有重要价值。     

开发高灵敏度血痕发光试剂用于法医现场检测

目的开发高灵敏度血痕发光试剂用于法医现场检测。方法本项目通过借鉴ECL发光的原理,通过化学电子链的乒乓共轭激活原理,使用均匀设计实验方法优化条件,合成多个新化合物,开发出新型高灵敏度血痕发光试剂。结果本项目开发的高灵敏度血痕发光试剂灵敏度高,发光时间长,在血液稀释1000倍的情况下,使用Chemi Scope3300化学发光成像系统读取荧光值,经过灰度转化最高值达到56,发光时间达到10分钟。结论本项目成功开发了高灵敏度血痕发光试剂,可以应用于法医现场检测。     

The Reliability of Pattern Classification in Bloodstain Pattern Analysis—PART 2: Bloodstain Patterns on Fabric Surfaces,

This study was designed to produce the first baseline measure of the reliability of bloodstain pattern classifications on fabric surfaces. Experienced bloodstain pattern analysts classified bloodstain patterns on pairs of trousers that represented three fabric substrates. Patterns also varied in type (impact, cast‐off, expiration, satellite stains from dripped blood, and transfer) and extent. In addition, case summaries that accompanied each pattern contained contextual cues that either supported the correct answer (i.e., positive bias), were misleading toward an incorrect answer (i.e., negative bias), or contained no directional information (i.e., neutral). Overall, 23% percent of the resulting classifications were erroneous. The majority (51%) of errors resulted from analysts misclassifying satellite stains from dripped blood. Relative to the neutral information, the positive‐bias information increased correct classifications and decreased erroneous classifications, and the negative‐bias information decreased correct classifications and increased erroneous classifications. The implications of these findings for BPA are discussed.     

Remote spectroscopic identification of bloodstains

Blood detection and identification at crime scenes are crucial for harvesting forensic evidence. Unfortunately, most tests for the identification of blood are destructive and time consuming. We present a fast and nondestructive identification test for blood, using noncontact reflectance spectroscopy. We fitted reflectance spectra of 40 bloodstains and 35 nonbloodstains deposited on white cotton with spectroscopic features of the main compounds of blood. Each bloodstain was measured 30 times to account for aging effects. The outcome of the blood measurements was compared with the reflectance of blood-mimicking stains and various body fluids. We found that discrimination between blood and nonblood deposited on white cotton is possible with a specificity of 100% and a sensitivity of 98%. In conclusion, a goodness of fit between the sample's reflectance and the blood component fit may allow identification of blood at crime scenes by remote spectroscopy.     

基于紫外可见积分球反射光谱法鉴定血痕经历时间

目的建立一种快速鉴定血痕陈旧度的方法。方法在实验室条件(20℃、25℃、30℃)下,使用UV-2450型紫外可见分光光度计,利用反射附件ISR-240A积分球,以BaSO_4标准白板做参比,间隔一定时间测定健康人耳静脉血血痕纱布的反射光谱,采集特定波长反射率R_(541)、R_(577),计算R_(541)/R_(577)值,使用SPSS 17.0软件进行直线拟合与回归分析。结果一定条件下8 h内,血痕经历时间与其特定波长紫外可见反射率比值回归分析的R~2均大于0.8,回归方程成立,血痕经历时间与R_(541)/R_(577)值具有高度相关性。结论所建立的方法简便、快速、无损,可靠性好,可以对实验室条件下8 h内血痕经历时间进行鉴别。     

Analysis of Hypodermic Needles and Syringes for the Presence of Blood and Polydimethylsiloxane (Silicone) Utilizing Microchemical Tests and Infrared Spectroscopy

Suspect hypodermic needles and syringes were seized from an unlicensed individual who was allegedly injecting patients with silicone (polydimethylsiloxane [PDMS]) for cosmetic enhancement. Since control syringe barrels and needles often contain an interfering PDMS lubricant, a risk for false positives of foreign PDMS exists. The focus of this report was to minimize this risk and determine a quick and reliable test for the presence of blood in PDMS matrices. Using ATR‐FT‐IR spectroscopy, the risk for false‐positive identification of foreign PDMS was reduced by (i) overfilling the sampling aperture to prevent spectral distortions and (ii) sampling a region of the suspect syringe/needle assembly where manufacturer‐applied PDMS is not typically located. Analysis for blood indicated that the Teichman microchemical test was effective for detecting blood in the presence of PDMS. Overall, detecting PDMS established intent and detecting blood established that the needle containing the PDMS had been used for injection.     

微量生物物证提取套装在现场微量血痕DNA检验中的应用

目的探讨微量生物物证提取套装应用于提取现场微量血痕DNA的检验效果。方法将静脉血制成地面血痕。分别应用微量生物物证提取套装法和普通法提取血痕。分别于恒温摇床放置2、24、48、72、96h(每组50份)进行血痕DNA检验,对比各组检验结果。结果恒温摇床上分别放置24、48、72、96h后,微量生物物证提取套装法的DNA检出率(分别为100.00%、100.00%、100.00%、96.00%)均高于普通法(分别为62.00%、26.00%、10.00%、0),差异均具有统计学意义(P<0.05)。恒温摇床上放置2h,两种方法的DNA检出率差异无统计学意义(P>0.05)。结论微量生物物证提取套装可有效提升放置时间较久的现场微量血痕的检出率和检出时限。     

Analyzing the Dynamics and Morphology of Cast‐off Pattern at Different Speed Levels Using High‐speed Digital Video Imaging

During a bloodstain pattern analysis, one of the essential tasks is to distinguish between different kinds of applied forces as well as to estimate their level of intensity. In this study, high‐speed digital imaging has been used to analyze the formation of cast‐off patterns generated by a simulated backswing with a blood‐bearing object. For this purpose, 0.5 mL blood was applied evenly over the last 5 cm of a blade simulant. Bloodstains were created through the controlled acceleration of a backswing at different speed levels between 1.1 m/sec and 3.8 m/sec. The flight dynamics of blood droplets were captured with an Olympus^® i‐Speed 3 high‐speed digital camera with a Nikon^® AF Nikkor 50 mm f/1.8 D lens and analyzed using the Olympus i‐Speed 3 Viewer software. The video analysis showed that, during the backswing, blood droplets would move toward the lower end of the knifepoint and would be tangentially thrown off. These droplets impacted on the horizontal surface according to the arc of the swing. An increase in velocity led to longer cast‐off patterns with distinct morphological characteristics. Under laboratory conditions, bloodstain pattern analysis allows certain conclusions about the intensity of a backswing and provides instructions on the position of the offender. However, due to the number of unknown variables at a crime scene, such interpretation of cast‐off patterns is extremely limited and should be performed with extreme caution.     

Preliminary Observations on the Ability of Hyperspectral Imaging to Provide Detection and Visualization of Bloodstain Patterns on Black Fabrics

Abstract: The analysis of bloodstain patterns can assist investigators in understanding the circumstances surrounding a violent crime. Bloodstains are routinely subjected to pattern analysis, which is inherently dependent upon the ability of the examiner to locate and visualize bloodstain patterns on items of evidence. Often, the ability to properly visualize bloodstain patterns is challenging, especially when the stain patterns occur on dark and/or patterned substrates. In this study, preliminary research was performed to better understand how near‐infrared reflectance hyperspectral imaging (HSI) could be used to observe bloodstain patterns on commonly encountered black fabrics. The ability of HSI to visualize latent bloodstains on several commonly encountered substrates is demonstrated. The images acquired through HSI are of sufficient quality to allow for differentiation between stains produced from an impact mechanism or a transfer mechanism. This study also serves as a proof of concept in the differentiation of multiple staining materials. Because of its ability to generate spectral data, the data provide a preliminary separation of stains where more than one type of stain existed.     

Statistical Evaluation of Alternative Light Sources for Bloodstain Photography

Bloodstain photography is important in forensic applications, especially for bloodstain pattern analysis. This study compares the enhancement effect of bloodstain photography using three different types of light source: fluorescent white light, near‐ultraviolet (UV) light‐emitting diode (LED) light, and 410 nm LED light. Randomized complete block designs were implemented to identify the lighting that would statistically produce the best enhancement results for bloodstains on different types of surfaces. Bloodstain samples were prepared on white cotton, brown carpet, tar road, and wood. These samples were photographed in darkroom conditions using a Canon EOS 50D digital SLR camera, with Canon EFS 60 mm f/2.8 Macro USM lens. Two‐way analysis of variance and Fisher's least significant difference test were used to analyze the contrast of the images. The statistical analysis showed that 410 nm light is the best among the tested lights for enhancing bloodstains on the tested surfaces, where the contrast of bloodstain to background was the highest.